CN1268165A

CN1268165A - Detergent compositions comprising a specific cellulase and a hydrophobic bleach

Info

Publication number: CN1268165A
Application number: CN 97182371
Authority: CN
Inventors: J·L·P·贝蒂奥尔; G·M·拜勒利
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1997-07-11
Filing date: 1997-07-11
Publication date: 2000-09-27

Abstract

The present invention relates to laundry detergent compositions containing particles bleacher, which contains a fungal cellulase without the cellulose binding structure domain and having a best pH between 4-10, and a hydrophobic bleach activator, thus providing improved overall washing, outstanding washing to all kinds of stains/dirt, and improved whiteness performance results.

Description

The detergent composition that contains specific cellulase and hydrophobic bleach

Technical field

The present invention relates to contain the laundry detergent composition that contains the granular bleach agent of specific cellulase and hydrophobic bleach activator.

Background of invention

Detergent composition has comprised the complex combination of the active ingredient that satisfies some special requirement now: surfactant system, the enzyme that cleaning and fabric nursing effect are provided, SYNTHETIC OPTICAL WHITNER, builder system, suds suppressor, soil-suspending agent, stain remover, white dyes, softening agent, dispersion agent, dye transfer suppress compound, abrasive material, sterilant, spices, and their overall performance improved really in recent years.Existing detergent formulation especially comprises detergent enzyme and cellulase more particularly usually.

The activity of cellulase is meant wherein cellulosic fibre or dirt-carrying body by cellulase hydrolysis, and depends on the concrete function of cellulase, and it can be inscribe or circumscribed cellulase and hemicellulase separately.Cellulosic structure is by depolymerization or fragment into lessly, thereby is more water-soluble or dispersible part.Especially should activity cleaning, recovery, softness and the common feel characteristic of improving be provided to fabric to woven fabric structure.

It has been recognized that cellulolytic enzyme, promptly cellulase clean as the fabric of fabric and the usefulness of roughness reduction reagent for some time; WO89/09259, GB-A-2075028, GB-A-2095275 and GB-A-2094826 disclose and have contained cellulase to improve the detergent composition of scourability; GB-A-1368599 discloses the purposes that cellulase is used to reduce the cotton-containing fabrics roughness; US4435307 disclose by Humicola insolens with and be called cellulolytic enzyme that the cut of ACXI obtains as the purposes that reduces the roughness detergent additives.

EP-A-0269168 discloses the optimizing detergent composition that contains cellulase, and it is prepared in gentle alkaline pH scope, and fabric washing, fabric sofetening and the fabric nursing performance of combination are provided.

Be applicable to that specific cellulase of the present invention describes in WO91/17244, wherein having described selected high specific acitivity single component enzyme and wherein disclose can degraded cellulose or the enzyme of hemicellulose.

Same suitable is disclosed cellulolytic enzyme in WO95/02675, it has described the detergent composition that contains two kinds of cellulose components: first kind of cellulose components has the active of delaying type and can remove particulate fouling, second kind of cellulose components contains a plurality of structural domains, it comprises at least one on-catalytic structural domain that connects catalyst structure domain, and can clarify color, wherein at least a cellulose components is an one-component.Described enzyme-containing detergent compositions can provide sufficient color clarification simultaneously and remove particulate fouling, and it neither damaged after the wash(ing)cycle of limited number of times, does not also partly degrade and contains cellulosic fabric.

Suitable specific cellulase is the EGIII cellulase of describing among the WO94/21801 of disclosed Genencor on the 29th September in 1994 that is obtained by Trichoderma longibrachiatum.

Known enzyme, especially cellulase help to remove some stain from fabric in the prior art, yet they can not prove that to all types of spots and/or dirt be very effective.People know that already SYNTHETIC OPTICAL WHITNER is effective for remove stain from fabric.Especially laundry detergent composition can contain hydrophobic bleach activator usually and good greasy/oil-dirt/dirt removal effect is provided.

Therefore, the purpose of this invention is to provide the laundry detergent composition that contains the granular bleach agent, it provides the overall washing that improves, to the whiteness impact of performance of outstanding washing and the improvement of various types of stain.

The combination that we are surprised to find specific cellulase and hydrophobic bleach activator shown the overall washing that improves, to the whiteness impact of performance of the outstanding washing and the improvement of various types of stain.

Specific cellulase and combining of hydrophobic bleach activator have shown the best and the synergisticing performance of enzyme and SYNTHETIC OPTICAL WHITNER technology.In fact, the laundry detergent composition that contains SYNTHETIC OPTICAL WHITNER of the present invention not only provides bleachability, and good specific cellulase stability and performance is provided.

Summary of the invention

The present invention relates to contain the laundry detergent composition that contains the granular bleach agent of specific cellulase and hydrophobic bleach activator, thereby provide the overall washing that improves, the whiteness impact of performance of outstanding washing and the improvement of various types of stain.

The detailed description specific cellulase of invention

Main ingredient of the present invention is a specific cellulase, it is usually to press general composition weight meter 0.0001%-2%, more preferably 0.0005%-0.05%, most preferably the content of the pure enzyme of 0.001%-0.01% is included in the laundry detergent composition that contains the granular bleach agent of the present invention.

Be applicable to that specific cellulase of the present invention is obtained by fungal bacterial strain, is preferably selected from following organism: Humicola isolens or Trichoderma longibrachiatum, reseei or viride.Another feature of specific cellulase is to have the best pH of 4-10 and does not have cellulose binding domain (CBD).Term CBD is meant the aminoacid sequence that cellulase effectively can be incorporated into Mierocrystalline cellulose dirt-carrying body.

Example applicable to cellulose components of the present invention is:

The endoglucanase component, it with by Humicola isolens DSM 1800 obtain high-purity ^-The antibody generation immune response that the 50kD endoglucanase produces or it are being somebody's turn to do of the plain enzymic activity of display fibers ^-The homologue of 50kD endoglucanase or derivative; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT patent application WO91/17244, or the endoglucanase component, it with obtain by fusarium oxysporum (Fusarium oxysporum) DSM 2672 high-purity ^-The antibody generation immune response that 50kD (apparent molecular weight, amino acid is formed the 45kD that is equivalent to have the 2n glycosylation site) endoglucanase produces or it are being somebody's turn to do of the plain enzymic activity of display fibers ^-The homologue of 50kD endoglucanase or derivative; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT patent application WO91/17244.More preferably by the about 50kDa of approximate molecular weight, iso-electric point about 5.5 with contain 415 amino acid whose Humicola insolens, DSM1800 obtains.

Endoglucanase can be by the known microorganism that can produce cellulolytic enzyme, for example Humicola, bacillus, Trichederma, fusarium, myceliophthora (Myceliophtora), Phanerochaete, Schizophyllum (Schizophyllum), Penicillium, Aspergillus and Geotrichum (Geotricum) obtain or separate, and purifying.The component that obtains can be homology or xenogeneic, and preferred ingredient is a homologous.Yet the xenogenesis component that immunoreactive xenogenesis component and this xenogenesis component are obtained by peculiar microorganism takes place in the also preferred antibody that produces with the high-purity cellulose components with required character.

For example described in WO95/02675, another kind of suitable endoglucanase component has appended therein SEQ ID NO:2 or at WO91/17244, disclosed aminoacid sequence or have and described sequence at least 60% among the accompanying drawing 14A-E, preferably at least 70%, more preferably at least 75%, more preferably at least 80%, more preferably at least 85%, the especially described endoglucanase mutation of at least 90% homologous aminoacid sequence.

Described endoglucanase can also be with obtain by fusarium oxysporum (Fusariumoxysporum) DSM 2672 high-purity ^-Immunoreactive endoglucanase component takes place the antibody that 50kD (apparent molecular weight, amino acid is formed the 45kD that is equivalent to have the 2n glycosylation site) endoglucanase produces or it is the plain enzymic activity of display fibers ^-The homologue of 50kD endoglucanase or derivative.Preferred endoglucanase component has SEQ ID NO:3 appended in WO95/02675 or at WO91/17244, disclosed aminoacid sequence or have and described sequence at least 60% in the accompanying drawing 13, preferably at least 70%, more preferably 75%, more preferably at least 80%, more preferably 85%, the especially described endoglucanase mutation of at least 90% homologous aminoacid sequence.

Described endoglucanase component component by aspergillus oryzae (Aspergillus oryzae) with containing corresponding at the plasmid of the dna sequence dna of the aminoacid sequence of the SEQ ID NO:3 described in the WO95/02675 with use Taka promotor and AMG terminator to change the back preparation, this endoglucanase can be a homogeneity with the cation chromatography purifying, has pl＞9.The pl of this calculating is based on the amino acid composition and uses from Adv.Protein Chem.17,69-165 page or leaf (1962), and the PHKa value of C.Tanford., molar extinction coefficient is calculated as 58180.

Other suitable cellulase is at disclosed WO94/21801 on September 29th, 1994, the EGIII that is obtained by Trichoderma longibrachiatum that describes among the Genencor.The preferred cellulase that is used for laundry detergent composition of the present invention is to have 22-27kDa approximate molecular weight, a cellulase of the pH optimum value of the iso-electric point of 7.2-8.0 and 5.5-6.0 by what Trichoderma (Trichoderma spp) obtained.

In the present invention, term " homology " is meant the polypeptide by dna encoding, (for example pre-soaking and in 5 * SSC under some special conditions at 20% methane amide, 5 * Denhardt ' s solution, 50mM sodium phosphate, in the solution of the calf thymic DNA of pH6.8 and 50 μ g sex change sonications about 40 ℃ of prehybridizations 1 hour, subsequently in hybridization 18 hours in the same solution of 100 μ M ATP supplies under about 40 ℃) it with the identical probe hybridization of the DNA of this amino acid sequence encode endoglucanase.This term comprise by the C of native sequences and N end one of or both add one or more amino-acid residues, in native sequences, replacing one or more amino-acid residues on one or more positions, on the one or both ends of natural acid sequence or the one or more positions in the native sequences, insert in the one or more amino-acid residues of disappearance or the one or more positions derivative of the above-mentioned sequence that one or more amino-acid residues obtain at natural acid sequence.

Yet, be the industrial production cellulase preparation, preferably adopt recombinant DNA technology or other technology of comprising the adjusting of fermentation or comprising microbial mutation produces with the excess of guaranteeing required enzymic activity.This method and technology are as known in the art, can easily be carried out by those skilled in the art.

Above-mentioned enzyme can be any suitable source, for example plant, animal, bacterium, fungi and yeast source.The source can also be have a liking for mesomeric state or have a liking for limiting condition (extremophilic) (have a liking for cold, thermophilic, have a liking for pressure, have a liking for alkali, have a liking for acid, have a liking for halogen etc.).Pure or the impure form of these enzymes can both be used.At present, common practice is that enzyme through protein/genetic engineering technique modification agriotype is with their effectiveness of performance in cleaning composition of the present invention of optimizing.For example but design variable is to increase the consistency of the component that runs into usually in enzyme and the said composition.In addition, but design variable makes best pH, SYNTHETIC OPTICAL WHITNER or sequestrant stability, the catalytic activity etc. of enzyme variants can adapt to specific washing uses.

Under the situation of bleach stability, especially should note to note surface charge to the amino acid of oxidation-sensitive with for surfactant compatibility.The iso-electric point of this kind of enzyme can be passed through some charged amino acid whose substituting modification, for example increases iso-electric point and can help to improve consistency with anion surfactant.The stability of enzyme can be further by producing for example additional salt bridge and strengthening the calcium binding site to increase the sequestrant improved stability.SYNTHETIC OPTICAL WHITNER

Main ingredient of the present invention is the hydrophobic bleach activator in bleach system, wherein uses the bleach system of bleach-activating agent also to comprise peroxygen bleach as main ingredient, and it can discharge hydrogen peroxide in the aqueous solution.

It is conventionally believed that bleach-activating agent has been the anionic nucleophilic attack of oxyhydroxide to form peroxycarboxylic acid, the described oxyhydroxide negatively charged ion of crossing is produced by the hydrogen peroxide that forms gradually by peroxygen bleach.

Detergent composition of the present invention comprises SYNTHETIC OPTICAL WHITNER, hydrogen peroxide for example, and particle size is PB1, PB4 and the percarbonate of 400-800 micron.These bleaching components can comprise one or more oxygen bleaching agents and, according to selected SYNTHETIC OPTICAL WHITNER, one or more bleach-activating agents.If present, the oxygen bleaching compound exists with the content of about 1%-about 25% usually.

The hydrogen peroxide releasing agent can with bleach-activating agent; nonanoly acyloxy benzene sulfonate (NOBS for example; in US4412934, describe), 3; 5;-trimethyl acetyl oxygen base benzene sulfonate (ISONOBS describes in EP120591) or N-nonanoyl-6-aminocaprolc acid sulfophenylate (NACA-OBS describes in WO94/28106) are used in combination; they are crossed hydrolysis to form the peracid as active albic material, improved bleaching effect.Their sour form also can be used, for example at our pelargonamide of crossing oxydisuccinic acid of not examining description among the application USSN 08/136626, the pelargonamide or the nonanoyl oxygen base benzene peroxy acid of peroxide hexanodioic acid.Other suitable hydrophobic bleach activator is at Procter ﹠amp; The asymmetric acyclic imide bleach activators of disclosed following formula among the patent application US № 60/022786 (application on July 30th, 1996) that does not examine of Gamble and the № 60/028122 (application on October 15th, 1996): R wherein ₁Be C ₇-C ₁₃Saturated or the unsaturated alkyl of straight or branched, R ₂Be C ₁-C ₈Straight or branched saturated or unsaturated alkyl and R ₃Be C ₁-C ₄Saturated or the unsaturated alkyl of straight or branched.

The useful SYNTHETIC OPTICAL WHITNER that is used for detergent composition of the present invention; comprise peroxy acid and contain the bleach system of bleach-activating agent and peroxy bleaching compound, as the N-acyl lactam SYNTHETIC OPTICAL WHITNER in WO95/27773, described and in the application PCT/US95/07823USSN that we examine discloseder bleach-activating agents.

Hydrophobic bleach activator is usually to press general composition weight meter 0.1%-20%, preferred 1%-15%, the more preferably content of 2%-10% existence.Detergent component

The laundry detergent composition that contains the granular bleach agent of the present invention can also contain other detergent component.The definite character of these additional components and their add-on will be according to the physical form of composition and the character decisions of employed washing operation.

The laundry detergent composition that contains the granular bleach agent of the present invention can be paste, gel, piece, sheet, sprays, foam, powder or particle form, and particulate composition can also be " densification " form.

Composition of the present invention for example can be mixed with manual and machine laundry detergent composition, and it comprises the fabric softener composition that adds in laundry additive composition and the immersion that is applicable to dirty fabric and/or pretreated composition, the rinsing.Composition of the present invention preferably contains tensio-active agent and washing-aid compound and additional one or more detergent component simultaneously, and it is preferably selected from organic polymer, SYNTHETIC OPTICAL WHITNER, additional enzyme, suds suppressor, dispersion agent, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and corrosion inhibitor.Laundry composition also can contain the softening agent as additional detergent components.

When being mixed with laundry detergent composition, the composition that contains specific cellulase and hydrophobic bleach activator can provide fabric washing, decontamination, whiteness maintenance, softness, color outward appearance, dye transfer to suppress and the health effect.

Composition of the present invention also can be used as the detergent additives product.This additive product is used for replenishing or strengthening the performance of conventional detergent composition.

If desired, the density that contains the laundry detergent composition of granular bleach agent of the present invention is determined as the 400-1200 grams per liter under 20 ℃, preferred 600-950 grams per liter composition.

" densification " form of the present composition by density and, for composition, reflect best by the amount of mineral filler salt; Mineral filler salt is the conventional component of the detergent composition of powder type; In conventional detergent composition, filling salt is generally by general composition weight meter 17-35% to exist in a large number.

In compact composition, filling salt preferably is no more than 10% to be no more than 15% of total composition by composition weight meter, is most preferably not exceeding 5% amount existence.

Be selected from the vitriol and the muriate of basic metal and alkaline-earth metal as the mineral filler salt of indication in the composition of the present invention.Preferred filling salt is a sodium sulfate.Surfactant system

The laundry detergent composition that contains the granular bleach agent of the present invention contains surfactant system usually, and wherein tensio-active agent can be selected from nonionic and/or negatively charged ion and/or positively charged ion and/or both sexes and/or zwitter-ion and/or semi-polarity tensio-active agent.

Tensio-active agent exists with the amount of 0.1%-60% by weight usually.In the laundry detergent composition that contains the granular bleach agent of the present invention, more preferably add-on is 1%-35% by weight, most preferably 1%-30% by weight.

Tensio-active agent preferably be mixed with composition in the enzyme component compatibility that exists.In liquid or gelatinous composition, tensio-active agent most preferably is mixed with it is promoted, or does not destroy the stability of any enzyme in these compositions at least.

Be used for preferred surfactant system of the present invention and contain nonionic and/or the anion surfactant that one or more the present invention describe as tensio-active agent.

The polyoxyethylene of alkylphenol, polyoxypropylene and polyoxy croton condensation thing are suitable as the nonionogenic tenside of surfactant system of the present invention, wherein preferred polyoxyethylene condenses.These compounds comprise having and contain about 14 carbon atoms of about 6-, the alkylphenol of the alkyl of the straight or branched configuration of about 14 carbon atoms of preferably about 8-and the condensation product of alkylene oxide.In preferred embodiments, oxyethane equals about 25 moles of about 2-with every mole of alkylphenol, and more preferably from about the amount of about 15 moles of ethylene oxide of 3-exists.Commercial available such ionic surfactant pack is drawn together the Igepal that is sold by GAF company ^TMCO-630 is by Rohm ﹠amp; The Triton that Haas company sells ^TMX-45, X-114, X-100 and X-102.These tensio-active agents are commonly referred to alkylphenol alcoxylates (for example alkyl phenol ethoxylate).

The condensation product of the oxyethane that primary and secondary fatty alcohol and about 1-are about 25 moles is suitable as the nonionogenic tenside of nonionic surfactant system of the present invention.The alkyl chain of fatty alcohol can be a straight or branched, and uncle or secondary contains about 22 carbon atoms of the 8-that has an appointment usually.Preferably have and contain about 20 carbon atoms of about 8-, more preferably contain the alcohol of alkyl of about 18 carbon atoms of about 10-and the condensation product of about 10 moles of ethylene oxide of the about 2-of every mol of alcohol.Every mol of alcohol exists about 7 moles of ethylene oxide of about 2-, most preferably 2-5 moles of ethylene oxide in described condensation product.The example of commercial available such nonionogenic tenside comprises Tergitol ^TM15-S-9 (C ₁₁-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol ^TM24-L-6 NMW (C with narrow molecular weight distributions ₁₂-C ₁₄The condensation product of primary alconol and 6 moles of ethylene oxide), sell by Union Carbide Corp; Neodol ^TM45-9 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol ^TM23-3 (C ₁₂-C ₁₃The condensation product of straight chain alcohol and 3.0 moles of ethylene oxide), Neodol ^TM45-7 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol ^TM45-5 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 5 moles of ethylene oxide), by the sale of shell chemical company, Kyro ^TMEOB (C ₁₃-C ₁₅The condensation product of alcohol and 9 moles of ethylene oxide), by Procter ﹠amp; Gamble company sells; With Genapol LA 030 or 050 (C ₁₂-C ₁₄The condensation product of alcohol and 3 or 5 moles of ethylene oxide), sell by Hoechst.The preferred HLB scope of these products is 8-11, most preferably 8-10.

Also can be used as surfactant system of the present invention nonionogenic tenside be disclosed alkyl polysaccharide in the US4565647 of the Llenado of on January 21st, 1986 promulgation, it has and contains about 30 carbon atoms of about 6-, the hydrophobic grouping of preferred about 16 carbon atoms of about 10-with contain the 1.3-that has an appointment about 10, preferred about 1.3-about 3, the most preferably from about polysaccharide of about 2.7 sugar units of 1.3-, for example polysaccharide glycosides hydrophilic radical.Can use any recuding sugars that contains 5 or 6 carbon atoms, glucose for example, semi-lactosi and galactosyl can be used for substituting glucosyl part (hydrophobic group optionally is connected positions such as 2-, 3-, 4-, thereby obtains glucose or semi-lactosi with respect to glucoside or galactoside).Key can be between 2-, 3-, 4-and/or the 6-position of position of for example additional sugar unit and previous sugar unit between sugar.

Preferred APG has following formula:

R ²O (C _nH _2nO) _t(glycosyl) _xR wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein to contain the 10-that has an appointment about 18 for alkyl, about 14 carbon atoms of preferably about 12-; N is 2 or 3, preferred 2; T is 0-about 10, preferred 0; With x be that about 1.3-is about 10, preferably about 1.3-is about 3, most preferably from about 1.3-about 2.7.Glycosyl is preferably obtained by glucose.For preparing these compounds, at first form alcohol or alkyl polyethoxye alcohol, form glucoside (being connected the 1-position) with glucose or source of glucose reaction subsequently.Other glycosyl units can be connected between its 1-position and previous glycosyl units 2-, 3-, 4-and/or the 6-position, preferably mainly in the 2-position subsequently.

Oxyethane also is suitable as additional nonionic surfactant system of the present invention with the condensation product of the hydrophobic grouping that forms by condensed epoxy propane and propylene glycol.The hydrophobic part of these compounds preferably has about 1500 to about 1800 molecular weight, and shows the water insoluble.Adding polyoxyethylene group in this hydrophobic part will increase the water-soluble of branch subpopulation, and it is the about 50% of condensation product gross weight that the fluid characteristics of product is retained to polyoxyethylene content, and this is equivalent to condensation up to about 40 moles oxyethane.Such examples for compounds comprises some commercially available Plurafac ^TMLF404 and Pluronic ^TMTensio-active agent is sold by BASF.

Be suitable as equally nonionic surfactant system of the present invention nonionogenic tenside be oxyethane and the condensation product of the product that obtains by propylene oxide and reacting ethylenediamine.The hydrophobic grouping of these products is made up of the reaction product of quadrol and excessive propylene oxide, 2500 to about 3000 the molecular weight of having an appointment usually.This hydrophobic grouping and ethylene oxide condensation are to making condensation product contain the polyoxyethylene of about by weight 40%-about 80% and having the degree of the molecular weight of about 5000-about 11000.The example of such nonionogenic tenside comprises some commercially available Tetronic ^TMCompound is sold by BASF.

The nonionogenic tenside that is preferably used as surfactant system of the present invention is the polyethylene oxide condensation compound of alkylphenol, condensation product, alkyl polysaccharide and their mixture of primary and secondary fatty alcohol and about 25 moles of ethylene oxide of about 1-.The C that most preferably contains 3-15 oxyethyl group ₈-C ₁₄Alkyl phenol ethoxylate and the C that contains 2-10 oxyethyl group ₈-C ₁₈Alcohol ethoxylate (preferred C ₁₀On average) and their mixture.

Highly preferred nonionogenic tenside is the polyhydroxy fatty acid amide surfactant of following formula:

R ²-C (O)-N (R ¹)-Z is R wherein ¹Be H, or R ¹Be C _1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R ²Be C _5-31Alkyl and Z are the polyhydroxy alkyl chains with the straight-chain alkyl chain that is connected directly to few 3 hydroxyls, or their alkoxy derivative.Preferred R ¹Be methyl, R ²It is straight chain C _11-15Alkyl or C _16-18The alkyl or alkenyl chain, for example Oleum Cocois alkyl or their mixture and Z are by reducing sugar, for example glucose, fructose, maltose, lactose obtain in reduction amination.

Spendable suitable anion surfactant is linear alkylbenzene sulfonate, alkyl sulfonate surfactants, and it comprises C ₈-C ₂₀The linear ester of carboxylic acid (being lipid acid), it is according to " U.S. oiling association will ", the method gaseous sulfur trioxide sulfonation in 52 (1975) the 323-329 pages or leaves.Proper raw material will comprise the natural fat material that is obtained by Tallow, beef, palm wet goods.

The preferred alkyl sulfonate surfactants that is particularly useful for laundry applications comprises the alkyl sulfonate surfactants that structural formula is following:

R ³-CH (SO ₃M)-C (O)-OR ⁴R wherein ³Be C ₈-C ₂₀Alkyl, preferred alkyl or their combination, R ⁴Be C ₁-C ₆Alkyl, preferred alkyl or their combination, M is a positively charged ion, it and alkyl ester sulfonic acid form water-soluble salt.Suitable salt-forming cation comprises metal, for example sodium, potassium and lithium and replacement or unsubstituted ammonium cation, for example monoethanolamine, diethanolamine and trolamine.Preferred R ³Be C ₁₀-C ₁₆Alkyl, and R ⁴Be methyl, ethyl or sec.-propyl.Especially preferred is R wherein ³Be C ₁₀-C ₁₆The methyl ester sulfonate of alkyl.

Other suitable anion surfactant comprises alkyl sulfate surfactant, and it is formula ROSO ₃The water-soluble salt of M or acid, wherein R C preferably ₁₀-C ₂₄Alkyl preferably contains C ₁₀-C ₂₀The alkyl of moieties or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, M is H or positively charged ion, its can be alkali metal cation (for example sodium, potassium, lithium) or ammonium or replacement ammonium (methyl-, dimethyl-and trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and, for example quaternary ammonium cation that obtains of ethamine, diethylamine, triethylamine and their mixture etc.) by alkylamine.For low wash temperature (for example being lower than about 50 ℃), usually preferred C ₁₂-C ₁₆Alkyl chain, for the preferred C of higher wash temperature (for example being higher than about 50 ℃) _16-18Alkyl chain.

Other anion surfactant that is applicable to the washing purposes also can be included in the laundry detergent composition that contains the granular bleach agent of the present invention.They can comprise soap salt (comprise, the ammonium salt of sodium, potassium, ammonium and replacement for example, for example single-, two-and triethanolamine salt), C ₈-C ₂₂Uncle or secondary paraffin sulfonate, C ₈-C ₂₄Sulfonation poly carboxylic acid, C that alkene sulfonate, the pyrolysis product of describing in GB1082179 that passes through the sulfonation alkaline earth metal citrate prepare ₈-C ₂₄Alkyl polyglycol ether sulfate (containing 10 moles of ethylene oxide at the most); Alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol vitriol, alkylphenol oxyethane ether sulfate, paraffin sulfonate, alkylphosphonic, isethionate; for example, acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinate monoesters (especially saturated and unsaturated C ₁₂-C ₁₈Monoesters) and sulfosuccinate diester (especially saturated and unsaturated C ₆-C ₁₂Diester), the vitriol of acyl sarcosinate, alkyl polysaccharide, alkyl polyglucoside vitriol (the not Sulfated compound of nonionic described below) for example, chain primary alkyl sulfate and alkyl polyethoxye carboxylate salt, for example formula RO (CH ₂CH ₂O) _k-CH ₂COO ^-M ⁺Those, wherein, R is C ₈-C ₂₂Alkyl, k are the 1-10 integers, and M is water miscible salt-forming cation.Resinous acid and hydrogenated resin acid also are suitable, for example rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in or are obtained by Yatall MA.

Other example is described in " tensio-active agent and washing composition " (I and II volume, Schwartz, Perry and Berch).Also general description is at the US3929678 of the Laughlin of on December 30th, 1975 promulgation etc. for various these class tensio-active agents, and the 23rd hurdle the 58th walks in the 29th hurdle the 23rd row (classifying this paper reference as).

If comprise, it is about 40% that the laundry detergent composition that contains the granular bleach agent of the present invention contains about by weight 1%-usually, preferably about 3%-about 20% this analog anion surfactants.

The ten minutes preferred anionic surfactants tensio-active agent that comprises alkyl alkoxylated sulfate surfactant is formula RO (A) _mSO ₃The water-soluble salt of M or acid, wherein R is unsubstituted C ₁₀-C ₂₄Alkyl or contain C ₁₀-C ₂₄The hydroxyalkyl of moieties, preferred C ₁₂-C ₂₀Alkyl or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than zero, usually between about 0.5 to about 6, more preferably between about 0.5 to about 3, M is H or positively charged ion, and it can be the ammonium cation of metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement for example.The present invention thinks over alkyl ethoxylated sulfate and alkyl propoxylated sulphates.The specific examples of the ammonium cation that replaces comprise methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine, for example ethamine, diethylamine, triethylamine, the positively charged ion that their mixture etc. obtains etc.The tensio-active agent of illustrative is C ₁₂-C ₁₈Alkyl polyethoxylated (1.0) vitriol (C ₁₂-C ₁₈E (1.0) M), C ₁₂-C ₁₈Alkyl polyethoxylated (2.25) vitriol (C ₁₂-C ₁₈E (2.25) M), C ₁₂-C ₁₈Alkyl polyethoxylated (3.0) vitriol (C ₁₂-C ₁₈E (3.0) M) and C ₁₂-C ₁₈Alkyl polyethoxylated (4.0) vitriol (C ₁₂-C ₁₈E (4.0) M), wherein M is selected from sodium and potassium usually.

The laundry detergent composition that contains the granular bleach agent of the present invention also can contain positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent and nonionic except that above having described and/or anion surfactant.

Be applicable to that the cationic detersive tensio-active agent that the present invention contains the laundry detergent composition of granular bleach agent is the material that contains a long chain hydrocarbon groups.The example of this cats product comprises ammonium surfactant, for example alkyl trimethyl ammonium halogenide and have the tensio-active agent of following formula:

[R ²(OR ³) _y] [R ⁴(OR ³) _y] ₂R ⁵N ⁺X ^-R wherein ²Be alkyl or the alkyl benzyl that in alkyl chain, contains about 18 carbon atoms of the 8-that has an appointment, each R ³Be selected from-CH ₂CH ₂-,-CH ₂CH (CH ₃)-,-CH ₂CH (CH ₂OH)-,-CH ₂CH ₂CH ₂-and their mixture; Each R ⁴Be selected from C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, by connecting two R ⁴The benzyl rings structure that group forms ,-CH ₂CHOH-CHOHCOR ⁶CHOHCH ₂OH, wherein R ⁶Be that any hexose or molecular weight are lower than about 1000 hexose polymkeric substance and when y is not 0, are hydrogen; R ⁵With R ⁴Identical or R wherein ²Add R ⁵The total number of carbon atoms be no more than about 18 alkyl chain; Each y is that 0-is about 10, and the summation of y value is 0-about 15; With X be any compatible negatively charged ion.

Be applicable to that quaternary ammonium surfactant of the present invention has as shown in the formula (I):

Formula I wherein R1 is a short-chain alkyl (C6-C10) or as shown in the formula the alkyl amido alkyl of (II):

Formula IIy is 2-4, and is preferred 3, and wherein R2 is H or C1-C3 alkyl, and wherein x is 0-4, preferred 0-2, and most preferably 0, wherein R3, R4 and R5 are identical or different, can be the alkoxylated alkyl of short-chain alkyl (C1-C3) or following formula III, wherein X ^-Be counter ion, preferred halogenide, for example muriate or methylsulfate,

Formula III R6 is C ₁-C ₄With z be 1 or 2.

Preferred quaternary ammonium surfactant is the compound by formula I definition, wherein R ₁Be C ₈, C ₁₀Or their mixture, x=0, R ₃, R ₄=CH ₃And R ₅=CH ₂CH ₂OH.

Highly preferred cats product is the water-soluble quaternary ammonium compound with following formula that is used for the present composition:

R ₁R ₂R ₃R ₄N ⁺X ^-(i) R wherein ₁Be C ₈-C ₁₆Alkyl, each R ₂, R ₃And R ₄Be respectively C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, benzyl and-(C ₂H ₄O) _xH, wherein x is 2-5, X is a negatively charged ion.R ₂, R ₃Or R ₄In to be no more than one should be benzyl.R ₁The preferred alkyl chain length be C ₁₂-C ₁₅, especially wherein alkyl is a mixture that obtained by Oleum Cocois or palm-kernel fat or or chain length that OXO pure synthetic method obtain synthetic by alkene.R ₂, R ₃And R ₄Preferred group be methyl and hydroxyethyl, negatively charged ion X can be selected from halogenide, methylsulfate, acetate moiety and phosphate anion.

The example that is used for suitable formula (i) quaternary ammonium compound of the present invention comprises:

Oleum Cocois trimethyl ammonium muriate or bromide;

Oleum Cocois methyl dihydroxy ethyl ammonium muriate or bromide;

Decyl triethyl ammonium muriate;

Decyl dimethyl hydroxyl ethyl ammonium muriate or bromide;

C _12-15Dimethyl hydroxyl ethyl ammonium muriate or bromide;

Oleum Cocois dimethyl hydroxyl ethyl ammonium muriate or bromide;

Tetradecyl trimethyl ammonium Methylsulfate;

Dodecyl dimethyl hexadecyldimethyl benzyl ammonium muriate or bromide;

Dodecyl dimethyl (oxyethylene group) ₄Ammonium muriate or bromide;

Cholinesterase (formula (i) compound, wherein R ₁Be CH ₂-CH ₂-O-C (O)-C _12-14Alkyl and R ₂, R ₃And R ₄Be methyl);

Dialkylimidazolium quinoline [formula (i) compound].

Be used for US4228044 and EP000224 that other cats product of the present invention also is described in the Cambre of promulgation on October 14th, 1980.

The soft component of typical cationic fabric comprises the soft active substance of water-insoluble quaternary ammonium fabric, and the most frequently used is the ammonium chloride or the Methylsulfate of two chain alkyl chains.

Wherein the preferred cation softening agent comprises as follows:

1) two Tallow, beef alkyl dimethyl ammonium chlorides (DTDMAC);

2) dihydro Tallow, beef alkyl dimethyl ammonium chloride;

3) dihydro Tallow, beef dimethyl methyl ammonium sulfate;

4) VARISOFT TA100;

5) two oil base alkyl dimethyl ammonium chlorides;

6) two palmityl hydroxyethyl ammonio methacrylates;

7) stearyl benzyl dimethyl ammonium chloride;

8) Tallow, beef base trimethyl ammonium chloride;

9) hydrogenated tallow base trimethyl ammonium chloride;

10) C _12-14Alkyl hydroxy ethyl alkyl dimethyl ammonium chloride;

11) C _12-18Alkyl dihydroxy ethyl ammonio methacrylate;

12) two (stearoyl-oxy ethyl) alkyl dimethyl ammonium chlorides (DSOEDMAC);

13) two (Tallow, beef oxygen base ethyl) alkyl dimethyl ammonium chloride;

14) two Tallow, beef base imidazoles Methylsulfates;

15) 1-(2-Tallow, beef amido ethyl)-2-Tallow, beef base imidazoles Methylsulfate.

Biodegradable quaternary ammonium compound has been used as the quid pro quo of normally used two long alkyl chain ammonium chloride and Methylsulfate.This quaternary ammonium compound contains by functional group, long-chain alkane (alkene) base that is interrupted of carboxyl for example, and described material and the fabric sofetening composition that contains them are at many publications, and be for example open among EP-A-0040562 and the EP-A-0239910.

Quaternary ammonium compound of the present invention and amine precursor have as shown in the formula (I) or (II):

Wherein Q be selected from-O-C (O)-,-C (O)-O-,-O-C (O)-O-,-NR ⁴-C (O)-,-C (O)-NR ⁴-; R ¹Be (CH ₂) _n-Q-T ²Or T ³R ²Be (CH ₂) _m-Q-T ⁴Or T ⁵Or R ³R ³Be C ₁-C ₄Alkyl or C ₁-C ₄Hydroxyalkyl or H; R ⁴Be H or C ₁-C ₄Alkyl or C ₁-C ₄Hydroxyalkyl; T ¹, T ², T ³, T ⁴And T ⁵Be C independently ₁₁-C ₂₂Alkyl or alkenyl; N and m are the integers of 1-4; And X ^-It is the compatible negatively charged ion of softening agent.

The anionic unrestricted example compatible with softening agent comprises chlorion or methylsulfate.

Alkyl or alkenyl chain T ¹, T ², T ³, T ⁴And T ⁵Must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.Chain can be a straight or branched.

Tallow, beef is the convenience and the cheap source of chain alkyl and thiazolinyl material.T wherein ¹, T ², T ³, T ⁴And T ⁵The compound of representing the long-chain substance mixture of common Tallow, beef is especially preferred.

The specific examples that is applicable to the quaternary ammonium compound of aqueous fabric soft compound of the present invention comprises:

1) N, N-two (Tallow, beef base oxygen base ethyl)-N, N-alkyl dimethyl ammonium chloride;

2) N, N-two (Tallow, beef base oxygen base ethyl) N-methyl, N-(2-hydroxyethyl) Methylsulfate;

3) N, N-two (2-Tallow, beef base oxygen base-2-oxoethyl)-N, N-alkyl dimethyl ammonium chloride;

4) N, N-two (2-Tallow, beef base oxygen base-ethyl carbonyl-oxygen base ethyl)-N, N-alkyl dimethyl ammonium chloride;

5) N-(2-Tallow, beef base oxygen base-2-ethyl)-N-(2-Tallow, beef base oxygen base-2-oxoethyl)-N, the N-alkyl dimethyl ammonium chloride;

6) N, N, N-three (Tallow, beef base-oxygen base-ethyl)-N-ammonio methacrylate;

7) N-(2-Tallow, beef base-amino-2-oxoethyl)-N-(Tallow, beef base)-N, the N-alkyl dimethyl ammonium chloride; With

8) 1,2-two Tallow, beef base oxygen base-3-trimethyl ammonium propane chloride;

Mixture with any above-mentioned substance.

If comprise, it is about 25% that the laundry detergent composition that contains the granular bleach agent of the present invention contains by weight 0.2%-usually, preferably about 1%-about 8% this cats product.

Amphoterics also is applicable in the laundry detergent composition that contains the granular bleach agent of the present invention.These tensio-active agents can broadly be described as the aliphatic derivatives of the second month in a season or tertiary amine or heterocycle is secondary and the aliphatic derivatives of tertiary amine, and wherein aliphatic group can be a straight or branched.One of aliphatic series substituting group contains at least about 8 carbon atoms, and about 18 carbon atoms of about usually 8-and at least one aliphatic substituting group contain the anionic water solubilizing group, for example carboxyl, sulfonate radical, sulfate radical.The US3929678 of the Laughlin that examples of amphoteric surfactants was issued referring on December 30th, 1975 etc., the 19th hurdle 18-35 is capable.

If comprise, it is about 15% that the laundry detergent composition that contains the granular bleach agent of the present invention contains by weight 0.2%-usually, preferably about 1%-about 10% this amphoterics.

Zwitterionics also is applicable in the laundry detergent composition that contains the granular bleach agent of the present invention.These tensio-active agents can broadly be described as the derivative of derivative, the heterocycle second month in a season and the tertiary amine of secondary and tertiary amine, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.The US3929678 of the Laughlin that the example of zwitterionics was issued referring on December 30th, 1975 etc., the 38th row-22 hurdles, the 19th hurdle 48 row.

If comprise, it is about 15% that the laundry detergent composition that contains the granular bleach agent of the present invention contains by weight 0.2%-usually, preferably about 1%-about 10% this zwitterionics.

Semi-polar nonionic surfactants is the nonionogenic tenside of particular variety, and it comprises that the moieties that contains about 18 carbon atoms of about 10-and two are selected from the water-soluble amine oxides of the part of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl; Contain the water soluble oxidized phosphine that the alkyl of about 18 carbon atoms of about 10-and two are selected from the part of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl; Be selected from the water-soluble sulfoxide of the part of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl with the moieties that contains about 18 carbon atoms of about 10-and one.

Semi-polarity nonionic detergent tensio-active agent comprises the amine oxide surfactant with following formula: R wherein ³Be alkyl, hydroxyalkyl or alkyl phenyl or its mixture that contains about 22 carbon atoms of the 8-that has an appointment; R ⁴Be alkylidene group or hydroxy alkylidene or their mixture that contains about 3 carbon atoms of the 2-that has an appointment; X is 0-about 3; Each R ⁵It is the polyoxyethylene group that contains the alkyl or the hydroxyalkyl of about 3 carbon atoms of the 1-that has an appointment or contain about 3 ethylene oxide groups of the 1-that has an appointment.R ⁵Group can for example be interconnected to form ring structure by oxygen or nitrogen-atoms.

These amine oxide surfactants especially comprise C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₈-C ₁₂Alkoxyethyl dihydroxy ethyl amine oxide.

If comprise, it is about 15% that cleaning composition of the present invention contains by weight 0.2%-usually, about 10% semi-polar nonionic surfactants of preferably about 1%-.

The laundry detergent composition that contains the granular bleach agent of the present invention also contains the cosurfactant that is selected from uncle or tertiary amine.

Be used for suitable primary amine of the present invention and comprise formula R ₁NH ₂Amine, R wherein ₁Be C ₆-C ₁₂, preferred C ₆-C ₁₀Alkyl chain or R ₄X (CH ₂) _n, X is-O-,-C (O) NH-or-NH-, R ₄Be C ₆-C ₁₂Alkyl chain, n are 1 to 5, preferred 3.R ₁Alkyl chain can be a straight or branched, can preferably be less than 5 ethylene oxide moieties and be interrupted by 12 at the most.

The preferred amines of following formula of the present invention is positive alkylamine.Be used for suitable amine of the present invention and be selected from 1-hexylamine, 1-octylame, 1-decane and lauryl amine.Other preferred primary amine comprises C ₈-C ₁₀Oxygen base propylamine, octyloxy propylamine, 2-ethyl hexyl oxy propylamine, dodecyl amido propylamine and amido propylamine.

Be used for suitable tertiary amine of the present invention and comprise having formula R ₁R ₂R ₃The tertiary amine of N, wherein R ₁And R ₂Be C ₁-C ₈Alkyl chain or

R ₃Be C ₆-C ₁₂, preferred C ₆-C ₁₀Alkyl chain or R ₃Be R ₄X (CH ₂) _n, and X is-O-,-C (O) NH-or-NH-, R ₄Be C ₄-C ₁₂, n is 1 to 5, preferably 2-3.R ₅Be H or C ₁-C ₂Alkyl and x are 1-6.R ₃And R ₄It can be straight or branched; R ₃Alkyl chain can preferably be less than 5 ethylene oxide moieties and be interrupted by 12 at the most.

Preferred tertiary amine is R ₁R ₂R ₃N, wherein R ₁Be C ₆-C ₁₂Alkyl chain, R ₂And R ₃Be C ₁-C ₃Alkyl or

Wherein _RThe 5th, H or methyl and x=1-2.

The amidoamines of following formula equally preferably:

R wherein ₁Be C ₆-C ₁₂Alkyl; N is 2-4, and preferred n is 3; R ₂And R ₃Be C ₁-C ₄

The most preferred amine of the present invention comprises 1-octylame, 1-hexylamine, 1-decyl amine, 1-lauryl amine, C ₈-C ₁₀Oxygen base propylamine, N-Oleum Cocois 1-3 diaminopropanes, Oleum Cocois alkyl dimethyl amine, dodecyl dimethyl amine, dodecyl two (hydroxyethyl) amine, Oleum Cocois two (hydroxyethyl) amine, 2 moles of propenoxylated lauryl amines, 2 moles of propenoxylated octylames, dodecyl amido propyl-dimethyl amine, C ₈-C ₁₀Amido propyl-dimethyl amine and C ₁₀The amido propyl-dimethyl amine.

The most preferred amine that is used for the present composition is 1-hexylamine, 1-octylame, 1-decane, 1-lauryl amine.Especially wish it is oleyl amine, dodecyl amido propylamine and the Oleum Cocois amido propylamine of dodecyl dimethyl amine and dihydroxy ethyl Oleum Cocois alkylamine and 7 ethoxylations.Conventional detergent enzyme

Except specific cellulase of the present invention, the laundry detergent composition that contains the granular bleach agent also can contain one or more enzymes, and it provides scourability, fabric nursing and/or hygiene effect.

Above-mentioned enzyme comprises the enzyme that is selected from other cellulase, hemicellulase, peroxidase, proteolytic enzyme, glucoamylase, amylase, zytase, lipase, Phospholipid hydrolase, esterase, at, polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, Malanases, beta-glucanase, arabinofuranosidase/xylosidase, hyaluronic enzyme, chondroitinase, laccase or their mixture.

Preferably combination is to contain conventional suitable enzyme, as the laundry detergent composition that contains the granular bleach agent of proteolytic enzyme, amylase, lipase, at and/or other cellulase and one or more plant cell-wall degrading enzymes bonded mixtures.Laundry detergent composition of the present invention will preferably also contain and be obtained by Humicola insolens DSM 1800 ^-The 43kD endoglucanase.

Be used for other cellulase of the present invention and comprise bacterium or fungal cellulase.They preferably have the pH optimum value between the 5-12 and surpass the activity of 50CEVU (Mierocrystalline cellulose viscosity unit).Suitable cellulase is described in US4435307, the J61078384 of Barbesgoard etc. and WO96/02653, and they disclose the fungal cellulase that is produced by Humicola insolens, Trichoderma (Trichoderma), careless Rhizopus (Thielavia) and Sporothrix (Sporotrichum) respectively.EP739982 has described by the new isolating cellulase of genus bacillus kind.Suitable cellulase also is disclosed among GB-A-2075028, GB-A-2095275, DE-OS-2247832 and the WO95/26398.

The example of this other cellulase is the bacterial strain by Humicola insolens (Humicolagrisea var.thermoidea), especially the cellulase of humicola lanuginosa strain DSM 1800 generations.Other suitable cellulase is the plain enzymic activity of display fibers that obtained by Humicola insolens DSM1800 ^-The 43kD endoglucanase; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT patent application WO91/17243.Especially suitable cellulase is the cellulase with color nursing efficacy.The example of this cellulase is the cellulase of describing in the EP patent application № 91202879.2 (Novo) of application on November 6th, 1991.Carezyme and Celluzyme (Novo Nordisk A/S) are particularly useful.Also referring to WO91/17244 and WO91/21801.Other suitable cellulase with fabric nursing and/or scourability is described in WO96/34092, WO96/17994 and WO95/24471.

Described other cellulase adds in the detergent composition in the content by the pure enzyme of detergent composition weight 0.0001%-2% usually.

Peroxidase and oxygen source, for example percarbonate, perborate, persulphate, hydrogen peroxide etc. and be used in combination as the phenols substrate of bleaching synergy molecule.They are used for " solution bleaching ", promptly avoid the dyestuff removed by matrix in washing operation or pigment to be transferred in other matrix in washing soln.Peroxidase is known in the prior art, and it comprises, for example horseradish peroxidase, lignoenzyme and halo peroxidase, for example chlorine and bromoperoxidase.The detergent composition that contains peroxidase is open in the EP № 96870013.8 of the European patent application EP 91202882.6 of for example PCT International Application No. WO 89/099813, WO89/09813 and application on November 6th, 1991 and application on February 20th, 1996.Same suitable is laccase.

Synergistic agent exists with the content by general composition weight meter 0.1%-5% usually.The thiodiphenylamine that preferred synergistic agent is replacement and phenoxazine, lysivane propionic acid (PPT), 10-ethyl thiodiphenylamine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-first base phenoxazine (in WO94/12621, describing) and the cloves acid esters (the alkyl cloves acid esters that C3-C5 replaces) and the phenol that replace.SPC-D or Sodium peroxoborate are preferred hydrogen peroxide cources.

Described peroxidase adds in the detergent composition in the content by the pure enzyme of detergent composition weight 0.0001%-2% usually.

Other preferred enzyme that can comprise in the present invention comprises lipase, and the suitable lipase that is used for the washing composition purposes comprises the microorganism of Rhodopseudomonas, the lipase that Situ Ci Shi aeruginosa atcc 19.154 disclosed in GB1372034 obtains.Suitable lipase comprises the lipase that shows positive immunological cross-reaction with lipase antibody, and it is produced by microorganism Pseudomonas fluorescens IAM 1057.This lipase can be obtained by Amano Pharmaceutical Co.Ltd. (Nagoya, Japan), and commodity are called lipase P " Amano ", hereinafter referred to as " Amano-P ".Other suitable commercial lipases comprises Amano-CES, from Chromobacter viscosum, as the lipase from the Chromobacter viscosumvar.lipolyticum NRRLB 3673 of Toyo Jozo Co. (Tagata, Japan); The Chromobacter viscosum lipase that obtains by U.S.Biochemical Corp. (US) and Disoynth Co. (Holland); And the lipase that obtains by the gladiolus pseudomonas.Especially suitable lipase is lipase, for example M1Lipase ^RAnd Lipomax ^R(Gist-Brocades) and Lipolase ^RAnd LipolaseUltra ^RWhen (Novo), they are found in and are used in combination with composition of the present invention is very effective.Same suitable be the lipolytic enzyme of in WO94/03578, the WO95/35381 of EP258068, the WO92/05249 of Novo Nordisk and WO95/22615 and Unilever and WO96/00292, describing.

That same suitable is at [EC 3.1.1.50], and it is considered to the lipase of particular variety, does not promptly need the lipase of interface activation.In detergent composition, add at for example WO-A-88/09367 (Genencor); Describe among WO90/09446 (Plant Genetic System) and WO94/14963 and the WO94/14964 (Unilever).

Lipase and/or at add in the detergent composition of the present invention in the content by the pure enzyme of detergent composition weight 0.0001%-2% usually.

Suitable proteolytic enzyme is by the subtilysin of the special bacterial strain of subtilis and Bacillus licheniformis (subtilysin BPN and BPN ').A kind of suitable proteolytic enzyme is obtained by the bacterial strain that the whole pH scope at 8-12 has the bacillus of maximum activity, and it is developed by NovoIndustries A/S (Denmark), and with ESPERASE ^Sell, hereinafter referred to as " Novo ".The preparation of this kind of enzyme and similar enzyme is described in the GB1243784 of Novo.Other suitable proteolytic enzyme comprises the ALCALASE that is obtained by Novo ^, DURAZYM ^And SAVINASE ^With the MAXATASE that obtains by Gist-Brocades ^, MAXACAL ^, PROPERASE ^And MAXAPEM ^(Maxacal of protein engineering).Protease also comprises the modified bacteria serine protease, the proteolytic enzyme of description in the european patent application sequence number 87303761.8 (especially 17,24 and 98 pages) of on April 28th, 1987 application for example, it is referred to herein as " proteolytic enzyme B " and the proteolytic enzyme in the EP199404 of disclosed Venegas on the 29th October in 1986, it relates to the bacterial serine protease of modification, and it is referred to herein as " protease A ".Suitable is the proteolytic enzyme that is referred to herein as " proteolytic enzyme C ", it is the mutation of the alkaline serine protease that obtained by bacillus, wherein replace arginine with Methionin at 27, replace Xie Ansuan at 104 with tyrosine, replace l-asparagine and replace Threonine with L-Ala with Serine at 274 at 123.Proteolytic enzyme C is disclosed EP90915958.4 in 16 days Mays in 1991, corresponding to describing among the WO91/06637.The mutation of gene modification, especially the mutation of proteolytic enzyme C is also included among the present invention.

The preferred protease that is called " proteolytic enzyme D " is the carbonylic hydrolase mutation that has at the undiscovered aminoacid sequence of occurring in nature, be called as the name of the C.Ghosh of WO95/10591 and on October 13rd, 1994 application etc. described in the patent application of " bleaching composition that contains proteolytic enzyme " (US series number № 08/322677), it by in above-mentioned carbonylic hydrolase, be equivalent to+replace various amino-acid residues with different aminoacids on 76 positions, and preferred also in conjunction with replacing numbering+99 that are equivalent to be selected from according to the bacillus amyloliquefaciens subtilysin, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265 and/or+one or more amino-acid residues of 274 obtain by the precursor carbonylic hydrolase.

Being equally applicable to of the present invention is the proteolytic enzyme of describing in EP251446 and WO91/06637, the BLAP  that describes in WO91/02792 and their mutation described in WO95/23221.

Also can be referring to the high pH proteolytic enzyme that obtains by bacillus NCIMB40338 described in the WO93/18140A of Novo.The enzyme-containing detergent that comprises proteolytic enzyme, one or more other enzymes and a kind of reversible protease inhibitors has been described among the WO92/03529A of Novo.If desired, can be as Procter ﹠amp; The WO95/07791 of Gamble is described to obtain having the adsorptivity of reduction and the water-disintegrable proteolytic enzyme of increase.A kind of recombinant trypsin shape proteolytic enzyme that is applicable to washing composition of the present invention has been described among the WO94/25583 of Novo.Other suitable proteolytic enzyme is described in the EP516200 of Unilever.

Protease to be pressing composition weight meter 0.0001%-2%, preferred 0.001%-0.2%, and more preferably the content of the pure enzyme of 0.005%-0.1% adds in the detergent composition of the present invention.

Can comprise that amylase (α and/or β) is to remove the spot of carbohydrate-based.On February 3rd, 1994, the WO94/02597 of disclosed Novo Nordisk A/S described the diastatic cleaning composition of adding mutant.Same WO95/10603 referring to disclosed Novo NordiskA/S on the 20th in April nineteen ninety-five.Other amylase that becomes known for cleaning composition comprises α-and beta-amylase.α-Dian Fenmei is known in the prior art, is included in the amylase of describing among US5003257, EP252666, WO91/00353, FR2676456, EP285123, EP525610, EP368341 and the GB1296839 (Novo).Other suitable amylase is the stable enhanced amylase described among the disclosed WO96/05295 in 18 days Augusts in 1994 of Genencor disclosed WO94/18314 and on February 22nd, 1996 and as the amylase mutation that has additional modification in the intermediate parent that is obtained by Novo Nordisk A/S described among the disclosed WO95/10603 in April, 95.Same suitable amylase is described in EP277216, WO95/26397 and WO96/23873 (by Novo Nordisk).

The example of commercial α-Dian Fenmei product is the Purafect OxAm that is obtained by Genencor ^And Termamyl ^, Ban ^, Fungamyl ^And Duramyl ^, obtain by Novo NordiskA/S Denmark.WO95/26397 has described other suitable amylase: α-Dian Fenmei, it is characterized in that, and pass through Phadebas ^The alpha-amylase activity test determination, it has the Termamyl of ratio in 25 ℃-55 ℃ temperature range and under the pH of 8-10 value ^Live high at least 25% ratio of ratio live.Suitable is the above-mentioned diastatic mutation of describing in WO96/23873 (Novo Nordisk).In WO95/35382, describe having other amylolytic enzyme that improves character aspect activity level and thermostability and the greater activity horizontal integration.

Amylolytic enzyme to be pressing composition weight meter 0.0001%-2%, preferred 0.00018%-0.06%, and more preferably the content of the pure enzyme of 0.00024%-0.048% adds in the detergent composition of the present invention.

Above-mentioned enzyme can be any suitable source, plant, animal, bacterium, fungi and yeast source for example, source can also be have a liking for mesomeric state or have a liking for limiting condition (have a liking for cold, thermophilic, have a liking for pressure, have a liking for alkali, have a liking for acid, have a liking for halogen etc.).Pure or the impure form of these enzymes can both be used.At present, common practice is that enzyme through protein/genetic engineering technique modification agriotype is with their effectiveness of performance in cleaning composition of the present invention of optimizing.For example but design variable is to increase the consistency of the component that runs into usually in enzyme and the said composition.In addition, but design variable makes best pH, SYNTHETIC OPTICAL WHITNER or sequestrant stability, the catalytic activity etc. of enzyme variants can adapt to specific washing uses.

Under the situation of bleach stability, especially should note to note surface charge to the amino acid of oxidation-sensitive with for surfactant compatibility.The iso-electric point of this kind of enzyme can be passed through some charged amino acid whose substituting modification, for example increases iso-electric point and can help to improve consistency with anion surfactant.The stability of enzyme can further strengthen by producing for example additional salt bridge and strengthening calcium binding site increase sequestrant stability.Must be noted that cellulase especially, because most of cellulase has independent binding domains (CBD).The character of this kind of enzyme can change by the modification in these structural domains.

Described enzyme adds in the detergent composition of the present invention in the content by the pure enzyme of detergent composition weight 0.0001%-2%.Enzyme can be used as independent component (containing a kind of bead, particle, stabilising liq of enzyme etc.) or adds as the mixture (for example composite particles (cogranulate)) of two or more enzymes.

Other suitable detergent component that can add is the oxydasis scavenging agent, and it is described not examining in the european patent application 92870018.6 of application on January 31st, 1992.The example of this oxydasis scavenging agent is ethoxylation four ethylidene polyamine.

The WO9307263A of Genencor International and WO9307260A, the US3553139 of the McCarty of the WO8908694A of Novo and promulgation on January 5th, 1971 etc. has also described the method in various enzyme materials and their the adding synthetic detergent compositions.The US4507219 of the US4101457 of the Place of promulgation on July 18th, 1978 etc. and the Hughes of promulgation on March 26th, 1985 further discloses enzyme.The US4261868 of the Hora of on April 14th, 1981 promulgation etc. has disclosed the proenzyme material that is used for the liquid scrubbing prescription and they and has added method in this prescription.The enzyme that is used for washing composition can in all sorts of ways and be stablized.The US3600319 of the Gedge of on August 17th, 1971 promulgation etc. and October in 1986 Venegas on the 29th EP199405 and EP200586 the enzyme stabilization technique is disclosed and enumerates.The enzyme stabilising system is also for example described in US3519570.The WO9401532A of Novo has described the useful bacillus AC13 that can access proteolytic enzyme, zytase and cellulase.Color nursing and fabric nursing effect

Also can comprise the technology that color nursing efficacy type is provided.The example of these technology is the metal catalysts that are used for the color protection, and this metal catalyst is described in the european patent application of not examining 92870181.2.Dye-fixing agent, be used for crease-resistant and improve polyolefin dispersion, the spices of water receptivity and be used for that color nursing is handled and the amino-functional polymers of spices affinity is other example of color nursing/fabric nursing technology, and examine description among the patent application № 96870140.9 in application on November 7th, 1996.

Fabric softener also can add in the laundry detergent composition of the present invention.These reagent can be inorganic or organic types.Inorganic softening agent is the terre verte of for example describing in GB-A-1400898 and US5019292.The organic fabric softening agent comprises the water-insoluble tertiary amine as describing among GB-A1514276 and the EP-B0011340, the mixture of they and single C12-C14 quaternary ammonium salt in EP-B-0026527 and EP-B-0026528 open and as EP-B-0242919 in disclosed two long-chain acid amides.Other useful organic constituent of fabric sofetening system is included in disclosed high molecular weight polyethylene oxide material in EP-A-0299575 and 0313146.

The consumption of terre verte is usually at 2%-20% by weight, and more preferably in the scope of 5%-15%, this material mixes in the rest part that component adds prescription as doing.The organic fabric softening agent, for example water-insoluble tertiary amine or two long-chain acid amides materials are with 0.5%-5% by weight, usually the consumption of 1%-3% adds, and high molecular weight polyethylene oxide material and water-soluble cationic material be with 0.1%-2% by weight, and the consumption of 0.15%-1.5% adds usually.These materials add the spraying drying part of composition usually, though they can be more easily as doing mixed particle adding or being sprayed at as melt liquid on other solid ingredient of composition in some cases.Other SYNTHETIC OPTICAL WHITNER

Operable a kind of other oxygen bleaching agent comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and diperoxy 12 carbon docosandioic acids.This SYNTHETIC OPTICAL WHITNER is open in US4483781, US patent application 740446, EP0133354 and US4412934.Highly preferred SYNTHETIC OPTICAL WHITNER also is included in 6-amino in the ninth of the ten Heavenly Stems-6-oxo peroxide acid of describing among the US4634551.

Operable another kind of SYNTHETIC OPTICAL WHITNER comprises halogen bleaching agent.The example of hypohalite SYNTHETIC OPTICAL WHITNER for example comprises TCCA (Trichloroisocyanuric acid) and dichloroisocyanuric acid sodium and potassium and N-chlorine and N-bromoalkane sulphonamide.This material is usually in the weight 0.5-10% by final product, and preferably 1-5% adds by weight.

The hydrogen peroxide releasing agent can with other bleach-activating agent, for example tetra acetyl ethylene diamine (TAED) or penta-acetyl glucose (PAG) are used in combination, they are crossed hydrolysis and form peracid as active albic material, cause the bleaching effect that improves.Same suitable promoting agent is the acylations citrate, and is for example open in not careful european patent application 91870207.7.

The containing metal catalyzer that is used for whitener composition comprises cobalt-containing catalyst, five amine cobaltous acetate (III) salt and contain Mn catalyst, for example compound of in EPA549271, EPA549272, EPA458397, US5246621, EPA458398, US5194416 and US5114611, describing for example.The bleaching composition that contain peralcohol, contains manganese bleach catalysts and sequestrant is described in patent application № 94870206.3.The transition metal complex of ring rigidity ligand is a containing metal catalyzer preferred for the present invention mostly, and they are at Procter ﹠amp; The not careful patent application US № 60/040629 of the application in 7 days March in 1997 of Gamble; № 60/039915; № 60/,040 222; № 60/040156; № 60/040115; Describe among № 60/038714 and the № 60/039920.

SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is known in the art, can be used for the present invention.A kind of non-oxygen bleaching agent that cherishes a special interest comprises the photoactivation SYNTHETIC OPTICAL WHITNER, for example sulfonated zinc and/or aluminium phthalocyanine.These materials can be deposited on the dirt-carrying body in washing process.Under rayed and in the presence of oxygen, for example by clothes being hung in the daylight when dry, sulfonation zinc phthalocyanine phthalocyanine is activated, and the dirt-carrying body is bleached subsequently.Preferred zinc phthalocyanine and photoactivation bleaching method are described in US4033718.Detergent composition will contain about by weight 0.025%-1.25% sulfonation zinc phthalocyanine phthalocyanine usually.

The useful SYNTHETIC OPTICAL WHITNER that is used for detergent composition of the present invention, the bleach system that comprises peroxy acid and contain bleach-activating agent and peroxy bleaching compound is described in application WO95/27772, WO95/27774 that we examine and WO95/27775.Builder system

Composition of the present invention also can contain builder system.The builder system of any routine is applicable to the present invention, it comprises silico-aluminate material, silicate, multi-carboxylate, alkyl or alkenyl succsinic acid and lipid acid, material, for example edetate, diethylenetriamine pentamethylene acetate, metal ion chelation agent, for example aminopolyphosphonic acid salt, especially ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylenophosphonic acid(DTPP).Phosphate builders also can be used among the present invention.

Suitable washing assistant can be a mineral ion exchange material, normally inorganic hydrated aluminosilicate material, more particularly hydration synthetic zeolite, for example hydrated zeolite A, X, B, HS or MAP.

Other suitable inorganic builders material is a layered silicate, for example SKS-6 (Hoechst).SKS-6 is by water glass (Na ₂Si ₂O ₅) crystalline layered silicate formed.

The suitable multi-carboxylate of containing a carboxyl is included in disclosed lactic acid, oxyacetic acid and their ether derivant in belgian patent 831368,821369 and 821370.The multi-carboxylate of containing two carboxyls comprise succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid water-soluble salt and DE2446686 and 2446687 and US3935257 in the ether carboxylate described and the sulfinyl carboxylate salt of in belgian patent 840623, describing.The multi-carboxylate of containing three carboxyls especially comprises water-soluble citrate, aconitate and citraconate and succinate derivative, the carboxyl methoxy succinate of for example in GB1379241, describing, the newborn oxygen base succinate of in Holland's application 7205873, describing and the oxygen multi-carboxylate material of in GB1387447, describing, 2-oxa--1 for example, 1,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxyls is included in disclosed oxygen di-succinate, 1,1,2 among the GB1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group be included in GB1398421 and 1398422 and US3936448 in disclosed sulfo-succinic acid salt derivative and the sulfonation pyrolysis Citrate trianion in GB1082179, described, and it is open in GB1439000 to contain the substituent multi-carboxylate of phosphono.

Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene (cyclopentadienide) pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF) tetracarboxylic acid hydrochlorate, 1,2,3,4,5,6-hexane hexacarboxylic acid salt and polyhydroxy-alcohol, for example carboxymethyl derivant of Sorbitol Powder, mannitol and Xylitol.Aromatic multi-carboxy acid's salt is included in disclosed mellitic acid among the GB1425343, pyromellitic acid and phthalic acid derivative.

Wherein, preferred multi-carboxylate is that per molecule contains the hydroxycarboxylate of three carboxyls at the most, more specifically is Citrate trianion.

The preferred builder system that is used for the present composition comprises water-insoluble silico-aluminate washing assistant, for example zeolite A or layered silicate (SKS-6) and water-soluble carboxylate sequestrant, for example mixture of citric acid.

Other preferred builder system comprises water-insoluble silico-aluminate washing assistant, for example zeolite A and water-soluble carboxylate sequestrant, for example mixture of citric acid.The preferred builder system that is used for liquid detergent composition of the present invention comprises soap and multi-carboxylate.

But component part is used for other builder material of the builder system of particulate composition and comprises inorganic substance, for example alkaline carbonate, supercarbonate, silicate and organic substance, for example organic phosphonate, amino polyalkylene phosphonate and aminopolycanboxylic acid's salt.

Other suitable water-soluble organic salt is all or co-polymeric acids or their salt, and wherein poly carboxylic acid contains and is no more than at least two carboxyls that two carbon atoms are separated from each other.Such polymkeric substance is open in GB-A-1596756.The example of this salt is the multipolymer of the polyacrylate of MW2000-5000 and they and maleic anhydride, and this multipolymer has 20000-70000, especially about 40000 molecular weight.

Detergent builders salt is usually pressing composition weight meter 5%-80%, preferred 10%-70%, and the most common be the amount existence of 30%-60% by weight.Sequestrant

The laundry detergent composition that contains the granular bleach agent of the present invention also optionally comprises one or more iron and/or manganese sequestrant.This sequestrant can be selected from aminocarboxylate, amino phosphonates do, and aromatic chelator that polyfunctional group replaces and composition thereof hereinafter will define them.Although do not want to be limited by theory, we think that the effect of these materials is in part because they remove the excellent ability of iron and mn ion by forming the soluble chelating thing from washings.

The aminocarboxylate of the sequestrant of useful as selective comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their basic metal, ammonium and substituted ammonium salt and composition thereof.

When allowing to use the total phosphorus of low levels at least in detergent composition, amino phosphonates do also is adapted at being used as in the present composition sequestrant, and it comprises ethylenediamine tetraacetic (methylene phosphonic acid salt), is DEQUEST.This amino phosphonates do does not preferably comprise the alkyl or alkenyl more than about 6 carbon atoms.

The aromatic chelator that polyfunctional group replaces also is suitable for the present composition.US3812044 referring to the Connor of on May 21st, 1974 promulgation etc.This compounds of preferred sour attitude is the dihydroxyl disulfobenzene, as 1, and 2-dihydroxyl-3,5-disulfobenzene.

Be used for biodegradable cheating agent of the present invention and be preferably ethylenediamine disuccinate (" EDDS "), [S, S] isomer particularly, this is open in the US4704233 of the Hartman of promulgation on November 3rd, 1987 and Perkins.

Composition of the present invention can also contain and for example insoluble washing assistant, water-soluble methylglycine oxalic acid (MGDA) salt (or acid) that is used as sequestrant or auxiliary washing assistant that for example zeolite, layered silicate etc. use together.

If use, these sequestrants are generally the about 15 weight % of about 0.1%-of detergent composition of the present invention.More preferably, if use, these sequestrants are the about 3.0 weight % of about 0.1%-of said composition.Suds suppressor

The component of another selection is a suds suppressor, for example polysiloxane and silicon dioxide-poly-mixture of siloxanes.Polysiloxane can be expressed as alkylating polysiloxane material usually, and silicon-dioxide uses with the broken form of fine powder usually, for example various types of silicon-dioxide aerosols, xerogel and water drain silica.These materials can be used as particulate and add, and wherein advantageously water-soluble or water is dispersible, the nonsurfactant washing composition is gone up adding releasedly in the impermeable carrier to suds suppressor substantially.In addition, suds suppressor solubilized or be dispersed in the liquid vehicle adds by being sprayed on one or more other components.

Preferred polysiloxane Foam Control is open in the US3933672 of Bartollota etc.Other suds suppressor that especially is suitable for is the self-emulsifying polysiloxane suds suppressor of describing among the disclosed German patent application DTOS2646126 on April 28th, 1977.This examples for compounds is DC-544, is commercially obtained by Dow Corning, and it is polysiloxane-diol copolymer.Especially preferred Foam Control is the suds suppressor system that contains the mixture of polysiloxane oil and 2-alkyl chain triacontanol.Suitable 2-alkyl-alkanol is a 2-butyl octanol, and it obtains with trade(brand)name Isofol 12R commercial.

This suds suppressor system is described not examining in the european patent application 92870174.7 of application on November 10th, 1992.

Especially preferred polysiloxane Foam Control is described in the european patent application of not examining 92201649.8, and described composition can contain and forge manufacture-illegal porous silica, for example Aerosil ^RBonded polysiloxane/silica mixture.

Usually to press composition weight meter 0.001%-2%, the content of preferred 0.01%-1% by weight uses above-mentioned suds suppressor.Other

Can use other component of the laundry detergent composition that is used for containing the granular bleach agent, for example soil-suspending agent, stain remover, white dyes, abrasive material, sterilant, tarnish inhibitor, tinting material and/or encapsulate capsule or do not wrap capsular spices.

Especially suitable encapsulate capsule material is a water-soluble capsule, and described in GB1464616, it is made up of the matrix of polysaccharide and polyol.

Other suitable water-soluble encapsulate capsule material comprises the dextrin that the starch acid esters by the not gelationization of the dicarboxylic acid that replaces described in US3455838 obtains.These acid esters dextrin are preferably by starch, and for example nephrite rice, soft Chinese sorghum, sago, tapioca (flour) and potato prepare.The suitable example of described encapsulate capsule material comprises the N-Lok by National Starch preparation.N-Lok encapsulate capsule material is made up of modified corn starch and glucose.Starch is by adding simple function group substituted radical, for example octenyl succinic acid anhydride modification.

Antiredeposition and soil-suspending agent that the present invention is suitable comprise derivatived cellulose, for example methylcellulose gum, carboxymethyl cellulose and Natvosol and poly carboxylic acid or its salt all or multipolymer.Such polymkeric substance comprises previously mentioned as the polyacrylate of washing assistant and the multipolymer of maleic anhydride-acrylic copolymer and maleic anhydride and ethene, methylvinylether or methacrylic acid, and maleic anhydride accounts at least 20 moles of % of multipolymer.These materials are usually with 0.5%-10% by weight, and more preferably 0.75%-8% most preferably presses the amount of composition weight meter 1%-6% and uses.

Preferred white dyes is the negatively charged ion feature, the example is 4,4 '-two-(2-alcohol amido-4-anilino-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2-morpholino-4-anilino-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4 '; 4 "-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2-sulfonic acid list sodium, 4,4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethyl amino)-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(4-phenyl-2,1,3-triazole-2-yl) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethyl amino)-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 2-(stilbene radicals-4 "-(naphtho--1 '; 2 ': 4; 5)-1; 2; 3-triazole-2 "-sodium sulfonate and 4,4 '-two (2-sulfo group styryl) biphenyl.Highly preferred whitening agent is the concrete whitening agent of the european patent application 95201943.8 do not examined.

Other useful polymkeric substance is a polyoxyethylene glycol, and especially molecular weight is 1000-10000, more preferably 2000-8000, most preferably from about 4000 polymkeric substance.They are with 0.20%-5% by weight, and more preferably the amount of 0.25%-2.5% is used.The multi-carboxylate of these polymkeric substance and homopolymerization mentioned above or copolymerization is improving whiteness maintenance, fabric dust deposit and is being valuable aspect the scourability of earth, protein and oxidable dirt in the presence of transition metal impurity.

The stain remover that is used for the present composition is the conventional terephthalic acid and ethylene glycol and/or the unitary multipolymer of propylene glycol or the terpolymer of different arrangement modes.This polymkeric substance the common US4116885 that transfers the possession of and 4711730 and the open EP0272033 of european patent application in describe, according to EP-A-0272033, especially preferred polymkeric substance has following formula:

(CH ₃(PEG) ₄₃) _0.75(POH) _0.25[T-PO) _2.8(T-PEG) _0.4]

T (POH) _0.25((PEG) ₄₃CH ₃) _0.75Wherein PEG is-(OC ₂H ₄) O-, PO is (OC ₃H ₆O) and T be (pcOC ₆H ₄CO).

Equally of great use be modified poly ester, the random copolymers of dimethyl terephthalate (DMT), sulfoisophthalic acid dimethyl ester, ethylene glycol and 1-2 propylene glycol for example, end group mainly are made up of sulfosalicylic acid ester and less important monoesters by ethylene glycol and/or propylene glycol.Target is to obtain at two ends by the end capped polymkeric substance of sulfosalicylic acid ester group, and in the present invention, most of above-mentioned multipolymer of the present invention " mainly " is by sulfosalicylic acid ester end-blocking.Yet some multipolymer will not be end capped fully, thereby their end group can be made up of the ethylene glycol and/or the third 1-2 glycol, and its " inferior strategic point " forms this material.

The polyester that the present invention selects contains about by weight 46% dimethyl terephthalate (DMT), by weight about 16% the third-1,2 glycol, about 10% ethylene glycol, about 13% sulfosalicylic acid dimethyl ester and about by weight 15% sulfoisophthalic acid by weight by weight, its molecular weight is about 3000.Polyester and their preparation method describe in detail in EPA311342.

The enzyme that the known free chlorine that exists in tap water of people promptly exists in the inactivation detergent composition.Therefore, use chlorine scavenger to press the content of general composition weight meter more than 0.1% in prescription, for example perborate, ammonium sulfate, S-WAT or polymine will provide the stability of the improvement of detergent enzyme in washing process.The composition that contains chlorine scavenger is described in the european patent application 92870018.6 of application on January 31st, 1992.

Be used for the present invention so that additional degrease performance to be provided as oxyalkylated multi-carboxylate by the polyacrylate preparation.This material is at WO91/08281 and PCT90/01815 page 4 and describe in each page later on, classifies this paper reference as.Contain the polyacrylate of the oxyethyl group side chain in every 7-8 acrylate unit at these materials chemically.Side chain has formula-(CH ₂CH ₂O) _m(CH ₂) _nCH ₃, wherein m is 2-3, n is 6-12.The side chain ester is connected in polyacrylate " skeleton " so that " comb shape " polymer-type structure to be provided.Molecular weight can change, but is generally about 2000-about 50000.This alkoxylate multi-carboxylate can account for about 0.05%-about 10% of present composition weight.Dispersion agent

The laundry detergent composition that contains the granular bleach agent of the present invention also can contain dispersion agent: suitable water-soluble organic salt is all or co-polymeric acids or its salt, and wherein poly carboxylic acid contains and is no more than at least two carboxyls that two carbon atoms separate.

Such polymkeric substance is open in GB-A-1596756.The example of this salt is the multipolymer of the polyacrylate of MW2000-5000 and they and maleic anhydride, and this multipolymer has the molecular weight of 1000-100000.

Especially, the multipolymer of acrylate and methacrylate, for example molecular weight is that 4000 480N can add by the content of composition weight meter 0.5-20% in the laundry detergent composition that contains the granular bleach agent of the present invention.

Composition of the present invention can contain calcium soap peptizing agent compound, and it has as what give a definition and is no more than 8, preferably is no more than 7, is most preferably not exceeding 6 lime soap dispersing power (LSDP).Calcium soap peptizing agent compound preferably exists with the amount of 0%-20% by weight.

The various measuring results of calcium soap peptizing agent effect provide by lime soap dispersing agent ability (LSDP), it is by using at article H.C.Borghetty and C.A.Bergman, and the calcium soap distributed test of describing in the 88-90 page or leaf of J.Am.Oil.Chem.Soc. the 27th volume is measured.This calcium soap distributed test method is extensive use of by the practitioner in this area, and is relevant with for example following comment; W.N.Linfield, tensio-active agent science book series (Surfactant scienceSeries), the 7th volume, page 3; W.N.Linfield, Tenside surf.det. the 27th volume, 159-163 page or leaf (1990) and M.K.Nagarajan, W.F.Masler, Cosmetics and Toiletries, the 104th volume, 71-73 page or leaf (1989).LSDP is at 333ppm lime carbonate (calcium: magnesium=3: 2) disperse the required dispersion agent of the calcium soap settling that formed by the 0.025g sodium oleate and the % weight ratio of sodium oleate in the 30ml water of equivalent hardness.

Tensio-active agent with good calcium soap peptizing agent ability comprises some amine oxide, trimethyl-glycine, sultaine, alkyl ethoxy sulfate and ethoxylated alcohol.

Having LSDP is no more than 8 the example that is used for tensio-active agent of the present invention and comprises C ₁₆-C ₁₈Dimethyl oxidation amine, average degree of ethoxylation are the C of 1-5 ₁₂-C ₁₈Alkyl ethoxy sulfate, especially average degree of ethoxylation are 3 C ₁₂-C ₁₅Alkyl ethoxy sulfate surfactant (LSDP=4) and average degree of ethoxylation are the C of 12 (LSDP=6) or 30 ₁₄-C ₁₅Ethoxylated alcohol is sold with trade(brand)name Lutensol A012 and Lutensol A030 respectively by BASF GmbH.

Be applicable to polymerization calcium soap peptizing agent of the present invention at M.K.Nagarajan, W.F.Masler at Cosmetics and Toiletries, the 104th the volume, describe in the article in the 71-73 page or leaf (1989).

The hydrophobic bleach agent is the amino caproyl of 4-[N-capryloyl-6-for example] benzene sulfonate; the amino caproyl of 4-[N-nonanoyl-6-] benzene sulfonate, the amino caproyl of 4-[N-decanoyl-6-] benzene sulfonate and their mixture and nonanoly acyloxy benzene sulfonate also can be used as calcium soap peptizing agent compound with hydrophilic/hydrophobic SYNTHETIC OPTICAL WHITNER preparation.Dye transfer suppresses

The laundry detergent composition that contains the granular bleach agent of the present invention also comprises the dyestuff that is suppressed at the dissolving that runs in the fabric washing operation that includes yarn dyed fabric and suspension is transferred to another kind of fabric from a kind of fabric compound.The polymeric dye transfer inhibitor

The laundry detergent composition that contains the granular bleach agent of the present invention also contains 0.001%-10% by weight, preferred 0.01%-2%, more preferably 0.05%-1% polymeric dye transfer inhibitor.In the laundry detergent composition that contains the granular bleach agent, add described polymeric dye transfer inhibitor so that on the fabric that the dye transfer of inhibition zone yarn dyed fabric is extremely therewith washed.In washing process, before the fugitive dye that washes out from DYED FABRICS had an opportunity to contact other article, this polymkeric substance had the ability that cooperates or adsorb this fugitive dye.

Especially suitable polymeric dye transfer inhibitor is multipolymer, polyvinylpyrrolidonepolymers polymers, Ju Yi Xi oxazolidinone and the polyvinyl imidazol or their mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.Add this polymkeric substance and also improved the performance of enzyme of the present invention.

A) polyamine N-oxide pllymers

The polyamine N-oxide pllymers that is suitable for contains the unit with following structural formula: Wherein P is polymerisable unit, and the R-N-O group can the coupled or wherein polymerisable unit of R-N-O group component part or both combinations.

A is

-O-,-S-,-N-; X is 0 or 1;

R is aliphatic series, aliphatic, the aromatic series of ethoxylation, heterocycle or alicyclic group or its any combination, the part that the nitrogen of N-O group can nitrogen coupled or wherein N-O group is these groups.

The N-O group can be represented by following general structural formula:

Wherein R1, R2 and R3 are aliphatic group, aromatic series, heterocycle or alicyclic group or their combination, x or/and y or/and z is 0 or 1, the part that the nitrogen of N-O group can be connected with it or wherein the nitrogen of N-O group constitutes these groups wherein.

The N-O group can be the part of polymerizable unit (P) or can link to each other with polymeric skeleton or both combination.

Wherein the suitable polyamine N-oxide of the part of N-O group formation polymerizable unit comprises polyamine N-oxide, and wherein R is selected from aliphatic series, aromatic series, alicyclic ring or heterocyclic group.

The above-mentioned polyamine N-oxide of one class comprises one group of polyamine N-oxide, and wherein the nitrogen of N-O group constitutes the part of R-group.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example the compound of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and their derivative.

Another kind of above-mentioned polyamine N-oxide comprises one group of polyamine N-oxide, and wherein the nitrogen of N-O group is connected in the R group.

Other suitable polyamine N-oxide is the polyamine oxide compound that is connected with polymerizable unit of N-O group wherein.

These polyamine N-oxide of preferred class are the polyamine N-oxide with general formula (I), and wherein R is aromatic series, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is the part of described R group.

The example of this compounds is the polyamine oxide compound, and wherein R is a heterogeneous ring compound, for example pyridine, pyrroles, imidazoles and their derivative.

The polyamine N-oxide of another preferred class is the polyamine oxide compound with general formula (I), and wherein R is aromatic series, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is connected in described R group.

The example of this compounds is the polyamine oxide compound, and wherein the R group can be aromatics, for example phenyl.

Can use any polymer backbone as long as the amine oxide polymers that forms is water miscible and has the dye transfer inhibition activity.The example of suitable polymeric skeleton is polyethylene, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and their mixture.

The ratio that common amine n-oxide polymkeric substance of the present invention has amine and amine n-oxide is 10: 1-1: 1000000.Yet the amount of the amine oxide group that exists in the polyamine oxide polymer can change by suitable copolymerization or by suitable N-degree of oxidation.The ratio of amine and amine n-oxide is preferably 2: 3-1: 1000000, more preferably 1: 4-1: 1000000, most preferably be 1: 7-1: 1000000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, and one of them monomer type is an amine n-oxide, and other monomer type is amine n-oxide or is not.The unitary PKa of the amine oxide of polyamine N-oxide＜10, preferred PKa＜7, more preferably PKa＜6.

The polyamine oxide compound can obtain by almost any extent of polymerization, and extent of polymerization is not crucial, as long as material has required water-soluble and dye suspension ability.

Molecular-weight average is generally 500-1000000; Preferred 1000-50000, more preferably 2000-30000, most preferably 3000-20000.

B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole

Be used for N-vinyl imidazole N-vinyl pyrrolidone polymer of the present invention and have 5000-1000000, the molecular-weight average of preferred 5000-200000.

The highly preferred polymkeric substance that is used for detergent composition of the present invention comprises the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, wherein said polymkeric substance has 5000-50000, more preferably 8000-30000, the most preferably molecular-weight average of 10000-20000.

Average molecular weight range passes through determination of light scattering by as Barth H.G. and Mays J.W. " chemical analysis " 113 volumes described in " modernism of polymer characterization ".

Highly preferred N-vinyl imidazole N-nvp copolymer has 5000-50000; More preferably 8000-30000; The molecular-weight average of 10000-20000 most preferably.

With above-mentioned molecular-weight average is that the N-vinyl imidazole N-vinylpyrrolidone copolymer of feature provides fabulous dye transfer inhibition activity, and does not influence the scourability with the detergent composition of its preparation unfriendly.

The mol ratio that N-vinyl imidazole N-vinylpyrrolidone copolymer of the present invention has N-vinyl imidazole and N-vinyl pyrrolidone is 1-0.2, more preferably 0.8-0.3, most preferably 0.6-0.4.

C) Polyvinylpyrolidone (PVP)

Detergent composition of the present invention can also use molecular-weight average about 400000 for about 2500-, and preferably about 5000-is about 200000, and more preferably from about 5000-is about 50000, most preferably from about the Polyvinylpyrolidone (PVP) of 5000-about 15000 (" PVP ").Suitable Polyvinylpyrolidone (PVP) commercial by ISP Corporation, New York, NY and Montreal, Canada is with ProductName PVP K-15 (viscosity molecular weight is 10000), PVP K-30 (molecular-weight average 40000), and PVP K-60 (molecular-weight average 160000) and PVP K-90 (molecular-weight average 360000) obtain.Can comprise Sokalan HP 165 and Sokalan HP 12 by other suitable Polyvinylpyrolidone (PVP) that BASF Cooperation obtains commercial; Polyvinylpyrolidone (PVP) known to the skilled in detergent applications (referring to for example EP-A-262897 and EP-A-256696).

D) Ju Yi Xi oxazolidinone:

Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.It is about 400000 that described Ju Yi Xi oxazolidinone has about 2500-, and preferably about 5000-is about 200000, and more preferably from about 5000-is about 50000, most preferably from about the molecular-weight average of 5000-about 15000.

E) polyvinyl imidazol:

Detergent composition of the present invention also can use polyvinyl imidazol as the polymeric dye transfer inhibitor, described polyvinyl imidazol has about 2500-about 400000, preferred about 5000-is about 200000, and more preferably from about 5000-is about 50000, most preferably from about the molecular-weight average of 5000-about 15000.

F) cross-linked polymer:

Cross-linked polymer is that wherein skeleton is interconnected to a certain degree polymkeric substance; These connections can be chemistry or physical properties, may have active group on skeleton or side chain; Cross-linked polymer is described in the 1035-1039 page or leaf at " polymer science magazine " 22 volumes.

In one embodiment, prepare cross-linked polymer by this way and make them form three-dimensional rigid structure, it can catch dyestuff in the hole that is formed by three-dimensional structure.In another embodiment, cross-linked polymer is caught dyestuff by swelling.

This cross-linked polymer is described in the patent application of not examining 94870213.9.Washing methods

Composition of the present invention can be used for any basically washing or purging method, and it comprises immersion process, pretreatment process and has the method for the rinse step that can add independent rinse aid composition.

Method of the present invention comprises fabric usually to contact with washing soln with mode hereinafter described.

Method of the present invention is carried out in washing process usually.Washing methods especially carries out between 10 ℃-60 ℃ preferably at 5 ℃-95 ℃.The pH of treatment soln is preferably 7-12.

Following embodiment is used to illustrate composition of the present invention, rather than limits or define in addition scope of the present invention.

In detergent composition, the content of enzyme represents that with the pure enzyme of general composition weight meter except as otherwise noted, detergent component is represented by general composition weight meter.The component symbol of abbreviation has following implication: LAS: straight chain C _11-13Sodium alkyl benzene sulfonate TAS: Tallow, beef sodium alkyl sulfate CxyAS: C _1x-C _1ySodium alkyl sulfate CxySAS: C _1x-C _1ySecondary (2,3) sodium alkyl sulfate CxyEz: with the C of average z moles of ethylene oxide condensation _1x-C _1yBe mainly straight chain

Primary alconol CxyEzS: with the C of average z moles of ethylene oxide condensation _1x-C _1ySodium alkyl sulfate QAS: R ₂.N ⁺(CH ₃) ₂(C ₂H ₄OH), R ₂=C ₁₂-C ₁₄QAS1: R ₂.N ⁺(CH ₃) ₂(C ₂H ₄OH), R ₂=C ₈-C ₁₁APA: C _8-10Amido propyl-dimethyl amine soap: by 80/20 mixture of Tallow, beef and coco-nut oil fatty acid obtain straight

Alkyl group carboxylic acid sodium STS: toluenesulfonic acid sodium salt CFAA: C ₁₂-C ₁₄Alkyl N-methyl glucose amide TFAA: C ₁₆-C ₁₈Alkyl N-methyl glucose amide silicate: amorphous sodium silicate (SiO ₂: Na ₂Zeolite A: the formula Na of O ratio=1.6-3.2) ₁₂(AlO ₂SiO ₂) ₁₂.27H ₂The hydrated sodium aluminosilicate of O, elementary

Particle size is 0.1-10 micron (weight of representing based on anhydrous benchmark) NaSKS-6: formula δ-Na ₂Si ₂O ₅The crystalline layered silicate Citrate trianion: citrate trisodium dihydrate, active 86.4%, particle size distribution

425-850 micron citric acid: Citric Acid, usp, Anhydrous Powder borate: Sodium Tetraborate carbonate: anhydrous sodium carbonate, particle size 200-900 micron supercarbonate: anhydrous sodium bicarbonate, particle size distribution is a 400-1200 micron vitriol: anhydrous sodium sulphate sal epsom: anhydrous magnesium sulfate STPP: tripoly phosphate sodium STPP MA/AA: 4: 1 acrylate/maleate random copolymerss, molecular-weight average are approximately

70000-80000MA/AA1: 6: 4 acrylate/maleate random copolymerss, molecular-weight average are approximately

10000AA: molecular-weight average is 4500 sodium polyacrylate polymer P B1: anhydrous sodium perborate monohydrate, nominal formula: NaBO ₂.H ₂O ₂PB4: sodium perborate tetrahydrate, nominal formula: NaBO ₂.3H ₂O.H ₂O ₂Percarbonate: anhydrous SPC-D, nominal formula: 2Na ₂CO ₃.3H ₂O ₂TAED: tetra acetyl ethylene diamine NOBS: nonanoly acyloxy benzene sulfonate; sodium-salt form NACA-OBS: (the amino caproyl of 6-nonanoyl) oxygen benzene sulfonate DTPA diethylene triaminepentaacetic acid(DTPA) HEDP: 1; 1-hydroxyl ethane di 2 ethylhexyl phosphonic acid DETPMP: diethyl triamine five (methylene radical) phosphonate, by Meng Shan all with trade(brand)name

Dequest 2060 sells EDDS: quadrol-N, N '-disuccinic acid, (S, S) isomer, the sodium-salt form photoactivation is floated: float with the white agent photoactivation of the capsular sulfonation zinc phthalocyanine phthalocyanine of dextrin polymer soluble bag: use white agent 1 proteolytic enzyme of the capsular sulphonation aluminum phthalocyanine of dextrin polymer soluble bag: with trade(brand)name Savinase, Alcalase, Durazym (Novo

Nordisk?A/S)，Maxacal，Maxapem(Gist-

Brocades) protease of Chu Shouing and at patent WO91/06637

And/or the proteolytic enzyme amylase of describing among WO95/10591 and/or the EP251446: at WO94/18314, the Genencor that describes among the WO96/05295 goes out

The Purafact Ox Am that sells ^Amylolytic enzyme; Termamyl ^,

Fungamyl ^And Duramyl ^, get by Novo Nordisk A/S

To with the amylase lipase of in WO95/26397, describing: by Novo Nordisk A/S with trade(brand)name Lipolase, Lipolase

Ultra and the steatolysis of selling with Lipomax by Gist-Brocades

Enzyme-cellulose enzyme: by the Mierocrystalline cellulose branch of Novo Nordisk A/S with the Endolase sale

Separate other fiber of enzyme: tie up plain lytic enzyme CMC by Novo Nordisk A/S with the fine plain enzyme that trade(brand)name Carezyme sells: Xylo-Mucine PVP: polyvinyl polymkeric substance, molecular-weight average are 60000.PVNO: polyvinylpyridine-N-oxide compound, molecular-weight average are 50000.PVPVI: vinyl imidazole and vinylpyrrolidone copolymer, molecular-weight average

Be 20000 whitening agent 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2: 4,4 '-two (4-anilinos-6-morpholino-1,3,5-triazines-2-yl)

Stilbene-2:2 '-disulfonic acid disodium polysiloxane: contain polydimethyl defoamer silicone foam control agent, described Foam Control and the described dispersion agent of siloxanes-oxyalkylene copolymers as dispersion agent

Ratio be 10: 1-100: 1.Suds suppressor: 12% polysiloxane/silicon-dioxide, 18% stearyl alcohol, 70% starch,

Particle form SRP1: the end capped polyester SRP2 of negatively charged ion: diethoxy poly terephthalic acid (1,2 inferior propyl ester) short chain block is poly-

Compound QEA: two ((C ₂H ₅O) (C ₂H ₄O) _n) (CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃) two

((C ₂H ₅O)-(C ₂H ₄O)) _n, n=20-30PEI wherein: polymine, molecular-weight average 1800, average degree of ethoxylation

Be 7 vinyloxy group residues of each nitrogen HMWPEO: high molecular weight polyethylene oxide PEGx: polyoxyethylene glycol, molecular weight xPEO: polyethylene oxide, molecular-weight average 5000 embodiment 1

Be prepared as follows high-density laundry detergent composition of the present invention:

I II III IV V

LAS 8.0 8.0 8.0 6.0 6.0

TAS - 0.5 - 1.0 0.1

C46(S)AS 2.0 2.5 - - -

C25AS - - - 4.5 5.5

C68AS 2.0 5.0 7.0 - -

C25E5 - - 3.4 4.6 4.6

C25E7 3.4 3.4 1.0 - -

C25E3S - - - 5.0 4.5

QAS - 0.8 - - -

QAS - - - 0.5 1.0

Zeolite A 18.1 18.0 14.1 19.0 18.1

Citric acid----2.5 carbonate 13.0 13.0 27.0 10.0 13.0Na-SKS-6----10.0 silicate 1.4 1.4 3.0 0.5 0.3 citrates-1.0---sulfate 25.1 26.1 26.1--magnesium sulfate 0.3---0.2MA/AA 0.3 0.3 0.3 1.0 1.0CMC 0.2 0.2 0.2 0.4 0.4PB4 4.0 9.0 5.0--percarbonate 5.0--18.0 17.0TAED 1.5 0.4 1.5 3.9 4.2NACA-OBS 1.0 2.0 1.0 1.0 1.0DETPMP 0.25 0.25 0.25--SRP1----0.2EDDS-0.25 0.4 0.5 0.5CFAA-1.0---HEDP 0.3 0.3 0.3 0.4 0.4QEA----0.5 cellulases 0.005 0.008 0.01 0.003 0.000

5 proteinase-10 .009,0.009 0.01 0.05 0.03 amylase, 0.002 0.002 0.002 0.008 0.008 other cellulase 0.000--0.000 0.000

777 lipase 0.006--0.01,0.01 photoactivation bleaching agent (ppm), 15 15 15 20 20PVNO/PVPVI-----brightening agent 1 0.09 0.09 0.09 0.09 0.09 spices 0.3 0.3 0.3 0.4 0.4 polysiloxane defoamers 0.5 0.5 0.5 0.3 0.3 density, as many as 100% embodiment 2 of g/l 850 850 850 850 850 microcomponents and a small amount of component

Prepare the following granular laundry detergent compositions that especially under European washing machine condition, uses of the present invention:

I II III IV

LAS 5.5 7.5 6.0 7.0

TAS 1.25 1.9 0.4 0.3

C24AS/C25AS - 2.2 5.0 2.2

C25E3S - 0.8 3.0 1.0

C45E7 3.25 - - 3.0

TFAA - - - -

C25E5 - 5.5 - -

QAS 0.8 - - -

QAS?1 - 0.7 1.0 0.7

STPP 19.7 - - -

Zeolite A-19.5 20.0 17.0

Na-SKS-6/ - 10.6 - -

Citric acid (79: 21)

Na-SKS-6 - - 10.0 10.0

Carbonate 6.1 21.4 10.0 18.0

Supercarbonate-2.0-2.0

Silicate 6.8-0.5-

Citrate trianion----

Vitriol 39.8--12.0

Sal epsom--0.2-

MA/AA 0.5 1.6 1.0 1.0

CMC 0.2 0.4 0.4 0.4

PB4 5.0 12.7 - -

Percarbonate--18.0 15.0

TAED 0.5 3.1 3.0 -

NACA-OBS 1.0 3.5 2.0 2.5

DETPMP 0.25 0.2 - 0.2

HEDP - 0.3 0.3 0.3

QEA - - 1.0 -

Cellulase 0.0008 0.005 0.0003 0.003

Proteinase-10 .009 0.03 0.05 0.02

Lipase 0.003 0.003 0.006 0.004

Other cellulase 0.0006 0.0006 0.0007 0.0007

Amylase 0.002 0.002 0.01 0.003

PVNO/PVPVI - - - -

PVP 0.9 1.3 - 0.9

SRP1 - - 0.2 -

Photoactivation SYNTHETIC OPTICAL WHITNER 15 27 20 20

(ppm)

Photoactivation SYNTHETIC OPTICAL WHITNER 15--

(1)(ppm)

Whitening agent 1 0.08 0.2 0.09 0.15

Whitening agent 2-0.04--

Spices 0.3 0.5 0.4 0.3

Polysiloxane defoamers 0.5 2.4 0.3 2.0

Density, g/l 750 750 750 750

Minor component and a small amount of component are at most to 100% embodiment 3

Be prepared as follows the detergent composition that is particularly useful for European washing machine wash conditions of the present invention.

I II III

The blowing powder

LAS 6.0 5.0 11.0

TAS 2.0 - -

Zeolite A 24.0--

STPP - 27.0 24.0

Vitriol 4.0 6.0 13.0

MA/AA 1.0 4.0 6.0

Silicate 1.0 7.0 3.0

CMC 1.0 1.0 0.5

Whitening agent 1 0.2 0.2 0.2

Silicone antifoam agent 1.0 1.0 1.0

DETPMP 0.4 0.4 0.2

Spraying liquid (Spray

On)

Whitening agent 0.02--

C45E7 - - -

C45E2 2.5 2.5 2.0

C45E3 2.6 2.5 2.0

Spices 0.5 0.3 0.5

Silicone antifoam agent 0.3 0.3 0.3

Dried additive

QEA - - -

EDDS 0.3 - -

Vitriol 2.0 3.0 5.0

Carbonate 6.0 13.0 15.0

Citric acid 2.5--

QAS1 0.5 - -

Na-SKS-6 10.0 - -

Percarbonate 18.5--

PB4 - 18.0 10.0

TAED 2.0 2.0 -

NACA-OBS 3.0 2.0 4.0

Cellulase 0.005 0.001 0.006

Proteinase-10 .03 0.03 0.03

Lipase 0.008 0.008 0.008

Amylase 0.003 0.003 0.003

Whitening agent 1 0.05--

Trace and a small amount of component are at most to 100% embodiment 4

Be prepared as follows granular detergent composition of the present invention:

I II III IV blows powder

LAS 23.0 7.0 7.0 7.0

TAS - - 1.0 -

C45AS 6.0 5.0 - -

C45AES - 1.0 - -

C45E35 - - 2.0 4.0

Zeolite A 10.0 14.0 10.0 10.0

MA/AA - - - 2.0

MA/AA1 7.0 - - -

AA - 3.0 3.0 3.0

Vitriol 5.0 14.3 15.0 19.3

Silicate 10.0 1.0 1.0 1.0

Carbonate 15.0 10.0 8.0 6.0

PEG4000 0.4 1.5 1.0 1.0

DTPA - 0.5 - 0.5

Whitening agent 2 0.3 0.3 0.1 0.3 spraying liquids

C45E7 - - 2.0 2.0

C25E9 3.0 - - -

C23E9 - 1.5 - 2.0

Spices 0.3 0.3 0.3 0.3 agglomerates

C45AS - 5.0 - 5.0

LAS - 2.0 - 2.0

Zeolite A-7.5-7.5

Carbonate-4.0-4.0

PEG4000 - 0.5 - 0.5

The dried additive of minor component (water etc.)-2.0-2.0

QAS - - 1.0 -

Citric acid--2.0-

PB4 - - 11.0 1.0

PB1 4.0 3.0 - -

Percarbonate--2.0 10.0

Carbonate-1.8 4.0 4.0

NOBS 4.0 6.0 1.0 0.6

Methylcellulose gum 0.2---

Na-SKS-6 8.0 - - -

STS - 2.0 1.0 -

Cumene sulfonic acid---2.0

Cellulase 0.005 0.0004 0.005 0.005

Proteinase-10 .02 0.02 0.02 0.02

Lipase 0.004 0.004 0.004 0.008

Amylase 0.003 0.002 0.003-

Other cellulase 0.0005 0.0005 0.0005 0.0005

PVPVI - - 0.5 0.1

PVP - - 0.5 -

PVNO - 0.5 - -

QEA - - 1.0 -

SRP1 0.2 0.3 0.2 -

Silicone antifoam agent 0.2 0.2 0.1-

Sal epsom-0.2 0.2-

Trace and a small amount of component are at most to 100% embodiment 5

Be prepared as follows detergent composition of the present invention:

I II

The base-material particle

Zeolite A 22.0 10.0

Vitriol 5.0 7.0

MA/AA - -

AA 1.6 -

MA/AA1 12.0 6.0

LAS 10.0 20.0

C45AS 7.0 7.0

C45AES 1.0 -

Silicate 1.0 10.0

Soap 2.0-

Whitening agent 1 0.2 0.2

Carbonate 9.0 10.0

PEG4000 1.0 -

DTPA 0.4 -

Spray liquid

C25E9 - 5.0

C45E7 1.0 -

C23E9 1.0 -

Spices 0.3-

Dried additive

Carbonate 10.0 8.0

PVPVI/PVNO - -

Cellulase 0.006 0.0005

Proteinase-10 .03 0.02

Lipase-0.008

Amylase-0.002

Other cellulase 0.0005 0.0002

NOBS 4.0 4.5

PB1 5.0 6.0

Vitriol 5.0 5.0

SRP1 0.4 -

Suds suppressor 0.5-

Trace and a small amount of component are at most to 100% embodiment 6

Be prepared as follows granular detergent composition of the present invention:

I II III

The blowing powder

Zeolite A 20.0-15.0

STPP - 20.0 -

Vitriol--5.0

Carbonate--5.0

TAS - - 1.0

LAS 6.0 6.0 6.0

C68AS 2.0 2.0 -

Silicate 3.0 8.0-

MA/AA 4.0 2.0 2.0

CMC 0.6 0.6 0.2

Whitening agent 1 0.2 0.2 0.1

DETPMP 0.4 0.4 0.1

STS--1.0 spraying liquid

C45E7 5.0 5.0. 4.0

Silicone antifoam agent 0.3 0.3 0.1

Spices 0.2 0.2 0.3 dried additives

QEA - - 1.0

Carbonate 14.0 9.0 10.0

PB1 1.5 2.0 -

PB4 17.5 12.0 12.0

TAED 2.0 2.0 2.0

NACA-OBS 1.0 1.0 1.0

QAS - - 1.0

Photoactivation SYNTHETIC OPTICAL WHITNER 15ppm 15ppm 15ppm

Na-SKS-6 - - 3.0

Cellulase 0.005 0.000 0.003

6

Proteinase-10 .03 0.03 0.007

Lipase 0.004 0.004 0.004

Amylase 0.006 0.006 0.003

Other cellulase 0.000 0.000 0.000

2 2 5

Vitriol 10.0 20.0 5.0

Density (g/l) 700 700 700

Trace and a small amount of component are at most to 100% embodiment 7

Prepare following detergent composition of the present invention:

I II III

The blowing powder

Zeolite A 14.0 15.0 15.0

Vitriol-5.0-

LAS 3.0 3.0 3.0

QAS - 1.5 1.5

DETPMP 0.4 0.2 0.4

EDDS - 0.4 0.2

CMC 0.4 0.4 0.4

MA/AA 4.0 2.0 2.0

Agglomerate

LAS 5.0 5.0 5.0

TAS 2.0 2.0 1.0

Silicate 3.0 3.0 4.0

Zeolite A 8.0 8.0 8.0

Carbonate 8.0 8.0 4.0

Spray liquid

Spices 0.3 0.3 0.3

C45E7 2.0 2.0 2.0

C25E3 2.0 - -

Dried additive

Citrate trianion 5.0-2.0

Supercarbonate-3.0-

Carbonate 8.0 14.0 10.0

TAED 6.0 2.0 5.0

PB1 14.0 7.0 14.0

NACA-OBS 1.0 1.0 1.0

PEO - - 0.2

Wilkinite--10.0

Cellulase 0.005 0.01 0.005

Proteinase-10 .03 0.03 0.03

Lipase 0.008 0.008 0.008

Other cellulase 0.001 0.001 0.001

Amylase 0.01 0.01 0.01

Silicone antifoam agent 5.0 5.0 5.0

Vitriol-3.0-

Density (g/l) 850 850 850

Trace and a small amount of component are at most to 100% embodiment 8

Prepare following detergent composition of the present invention:

I II

LAS 18.0 14.0

QAS 0.7 1.0

TFAA - 1.0

C23E56.5 - -

C45E7 - 1.0

C45E3S 1.0 2.5

STPP 32.0 18.0

Silicate 9.0 5.0

Carbonate 11.0 7.5

Supercarbonate-7.5

PB1 3.0 1.0

PB4 - 1.0

NOBS 2.0 1.0

DETPMP - 1.0

DTPA 0.5 -

SRP1 0.3 0.2

MA/AA 1.0 1.5

CMC 0.8 0.4

PEI - -

Vitriol 20.0 10.0

Sal epsom 0.2-

Cellulase 0.0005 0.008

Proteinase-10 .03 0.03

Amylase 0.008 0.007

Lipase 0.004-

Other cellulase 0.0003-

Photoactivation SYNTHETIC OPTICAL WHITNER 30ppm 20ppm

Spices 0.3 0.3

Whitening agent 1/2 0.05 0.02

Trace and a small amount of component are at most to 100% embodiment 9

Prepare following particle fabric detergent composition of the present invention, it has the ability of " soft in washing process ":

I II

C45AS - 10.0

LAS 7.6 -

C68AS 1.3 -

C45E7 4.0 -

C25E3 - 5.0

Oleum Cocois alkyl dimethyl hydroxyethyl chlorine 1.4 1.0

Change ammonium

Citrate trianion 5.0 3.0

Na-SKS-6 - 11.0

Zeolite A 15.0 15.0

MA/AA 4.0 4.0

DETPMP 0.4 0.4

PB1 15.0 -

Percarbonate-15.0

TAED 4.0 4.0

The as many as 100% of other cellulase 0.001-silicate 3.0 5.0 carbonate, 10.0 10.0 foam inhibitors 1.0 4.0CMC, 0.2 0.1 trace of NACA-OBS 1.0 1.0 terre verte 10.0 10.0HMWPEO-0.1 cellulases 0.005 0.01 proteinase-10 .02 0.01 lipase 0.02 0.01 amylase 0.03 0.005 and a small amount of components

Claims

1. laundry detergent composition that contains the granular bleach agent, it contains hydrophobic bleach activator and best pH is 4-10 and the fungal cellulase that does not have cellulose binding domain.

2. according to the laundry detergent composition that contains the granular bleach agent of claim 1, wherein said cellulase is by Humicola isolens, Trichoderma longibrachiatum, Trichoderma reseei and/or viride (Trichoderma viride) obtain.

3. according to the laundry detergent composition that contains the granular bleach agent of claim 1-2, the feature of wherein said cellulase also is to show below character:

(a) by Humicola insolens, DMS 1800 obtains;

(b) approximate molecular weight is about 50kDa;

(c) iso-electric point is about 5.5; With

(d) contain 415 amino acid.

4. according to the laundry detergent composition that contains the granular bleach agent of claim 1-2, the feature of wherein said specific cellulase also is to show below character:

(a) obtain by Trichoderma (Trichoderma spp);

(b) approximate molecular weight is 22-27kDa;

(c) iso-electric point is 7.2-8.0; With

(d) best pH is 5.5-6.0.

5. according to the laundry detergent composition that contains the granular bleach agent of claim 1-4, the content of wherein said cellulase is for pressing general composition weight meter 0.0001%-0.1%, preferred 0.0005%-0.05%, the more preferably pure enzyme of 0.001%-0.01%.

6. according to the laundry detergent composition that contains the granular bleach agent of claim 1-5, wherein the content of hydrophobic bleach activator is for pressing general composition weight meter 0.1%-20%, preferred 1%-15%, more preferably 2%-10%.

7. according to the laundry detergent composition that contains the granular bleach agent of above-mentioned arbitrary claim, wherein said hydrophobic bleach activator is selected from nonanoyl oxygen base benzene sulfonate, the amino hexylyloxy benzene sulfonate of nonanoyl, asymmetric acyclic imide and/or their mixture.

8. according to the laundry detergent composition that contains the granular bleach agent of above-mentioned arbitrary claim, it also contains the conventional detergent enzyme that is selected from other cellulase, proteolytic enzyme, amylase and/or lipase.

9. according to the laundry detergent composition that contains the granular bleach agent of claim 7, wherein said other cellulase is that DSM1800 obtains by Humicola insolens ^-The 43kD endoglucanase.

10. according to the laundry detergent composition that contains the granular bleach agent of above-mentioned arbitrary claim, it is the form of additive.

11. hydrophobic bleach activator and best pH are 4-10 and the purposes of fungal cellulase in the detergent for washing clothes that contains the granular bleach agent that does not have cellulose binding domain, so that the outstanding washing and the whiteness impact of performance to be provided.